Adhesives and related methods

ABSTRACT

Cure in place pressure sensitive adhesive compositions are described that comprise one or more of a bodying component, a structural diluent, a radical diluent as well as additives such as crosslinkers, external catalysts, photoinitiators and stabilizers/process aids. The bodying component can be acrylic or non-acrylic.

CROSS REFERENCE TO RELATED APPLICATION

The present application is a 371 of International Application No.PCT/US2013/064188, which was published in English on Apr. 17, 2014, andclaims priority from U.S. Provisional Application No. 61/711,386 filedon Oct. 9, 2012, both of which are incorporated herein by reference intheir entireties.

FIELD

The present subject matter generally relates to reactive oligomersand/or compounds blended with an acrylate or vinyl-acrylate basepolymer. In certain versions, a non-acrylate polymer is used in theblends. The blends result in a pressure sensitive adhesive (PSA) whichcontains a latent functionality on the oligomers and/or additives forcrosslinking in place. Crosslinking can be triggered by surfacecatalysis, UV irradiation, or other cure mechanisms.

Specifically, the present subject matter is directed to pressuresensitive adhesive compositions, and more particularly, to pressuresensitive adhesives having high adhesion over a wide temperature range.The subject matter is also directed to cure in place liquidcompositions. The subject matter is also directed to methods of formingand methods of using such compositions. The subject matter is furtherdirected to foam articles incorporating the compositions.

SUMMARY

The present subject matter is generally directed to pressure sensitiveadhesives which are cured in place by UV light, surface catalysis, orsome other mechanism, and which attain much higher strength than typicalPSAs. The adhesives are typically formed by blending reactive oligomerswith one or more high molecular weight acrylate polymers. An example isa blend of a silane functional acrylic polymer and a silyl terminatedpolyether. The blend is inherently tacky and can be cured by exposingthe blend to a compound containing an oligomeric silane such as may beprinted on a mating surface.

In one embodiment, the pressure sensitive adhesive or cure in placecomposition of the subject matter is formed from a blend comprising: (a)a reactive oligomer and (b) a high molecular weight acrylate polymer.The blend is inherently tacky and is cured by exposing the blend to acompound containing an oligomeric silane which may be introduced bybeing printed on a surface.

Another embodiment of the subject matter is a cure in place pressuresensitive adhesive comprising: (a) 20-80 weight percent (wt %) of abodying component comprising an acrylic base polymer having a molecularweight (Mw) of 5,000 to 1,000,000, in certain embodiments15,000-250,000, and in still other embodiments 15,000-100,000, (b) 5-50wt % of one or more structural diluents, (c) 10-80 wt % of one or moreradical addition diluents, (d) 0-4.0 wt % of one or more crosslinkers,(e) 0-4.0 wt % of one or more external catalysts, (f) 0.01-10 wt % ofone or more photoinitiators, and (g) 0-10.0 wt % of one or morestabilizer/process aids.

Yet another embodiment of the subject matter is a cure in place pressuresensitive adhesive comprising (a) 20-80 wt % of a bodying componentcomprising a base polymer having a Mw of 1,000 to 500,000, in certainembodiments 1,000-100,000, and in still other embodiments 1000-50,000,selected from the group consisting of polyolefins, polyvinyl aromatics,polyurethanes, polycarbonates, polyesters, polyethers, and combinationsthereof, (b) 5-50 wt % of one or more structural diluents, (c) 10-80 wt% of one or more radical addition diluents, (d) 0-1.0 wt % of one ormore crosslinkers, (e) 0-4.0 wt % of one or more external catalysts, (f)0.01-10 wt % of one or more photoinitiators, and (g) 0-10.0 wt % of oneor more stabilizer/process aids.

An additional embodiment of the present subject matter includes a curein place pressure sensitive adhesive comprising: (a) 20-80 wt % of anacrylic base polymer having a Mw of 100,000 to 1,000,000, and in certainembodiments 250,000-750,000, (b) 0-30 wt % of one or more tackifiers,(c) 5-40 wt % of one or more liquid reactive components, (d) 0-30 wt %of an acrylic-epoxy functional component and/or epoxy functional olefin,and (e) 0-2 wt % of a metal chelate crosslinker-catalyst and/or externalcatalyst.

An additional embodiment of the present subject matter includes a curein place pressure sensitive adhesive comprising: (a) 50-80 wt % of anacrylic base polymer having a Mw of 250,000-750,000, (b) 10-30 wt % ofone or more structural diluents, (c) 0-0.5 wt % of a metal chelatecrosslinker, (d) 0-2 wt % of one or more external catalysts, and (e)0-10 wt % of stabilizer/process aid.

An additional embodiment of the present subject matter includes a curein place pressure sensitive adhesive comprising: (a) 50-80 wt % of anacrylic base polymer having a Mw of 250,000-750,000, (b) 20-40 wt % ofone or more structural diluents, (c) 0-30 wt % of an optionalacrylic-epoxy functional component, (d) 0-0.5 wt % of a metal chelatecrosslinker, (e) 0-2 wt % of one or more external catalysts, and (f)0-10 wt % of stabilizer/process aid.

An additional embodiment of the present subject matter includes a curein place liquid comprising: (a) 5-70 wt % of a bodying componentcomprising an acrylic base polymer having a Mw of 5,000 to 1,000,000, incertain embodiments 15,000-250,000, and in still other embodiments15,000-100,000, (b) 5-40 wt % of one or more structural diluents, (c)30-95 wt % one or more radical addition diluents, (d) 0-10.0 wt % one ormore external catalyst, (e) 0-10 wt % one or more photoinitiators, (f)0-10 wt % one or more photosensitizer, and (g) 0-10 wt % stabilizer(s).

An additional embodiment of the present subject matter includes a curein place liquid comprising: (a) 5-50 wt % of a bodying componentcomprising an acrylic base polymer having a Mw of 15,000 to 100,000, (b)50-95 wt % of one or more structural diluents, (c) 0.01-10 wt % one ormore external catalysts, and (d) 0-10 wt % stabilizer/process aid.

An additional embodiment of the present subject matter includes a curein place liquid comprising (a) 30-70 wt % of a bodying componentcomprising an acrylic copolymer having a Mw of 15,000-100,000, (b) 7-70wt % of one or more structural diluents, (c) 7-70 wt % of one or moreradical addition diluents, (d) 2-10 wt % of one or more photoinitiators,(e) 0-1% of one or more antioxidants, and (f) 0-10 wt %stabilizer/process aid.

An additional embodiment of the present subject matter includes a curein place liquid comprising: (a) 5-70 wt % of a bodying componentcomprising an acrylic base polymer having a Mw of 5,000 to 1,000,000, incertain embodiments 15,000-250,000, and in still other embodiments15,000-100,000, (b) 5-80 wt % of one or more structural diluents, (c)5-70 wt % one or more radical addition diluents, (d) 0-5.0 wt % one ormore external catalysts, (e) 0-10 wt % of one or more photoinitiators,(f) 0-10 wt % of one or more photosensitizers, and (g) 0-10 wt %stabilizer/process aid.

An additional embodiment of the present subject matter includes a curein place liquid comprising: (a) 10-15 wt % of a bodying componentcomprising an acrylic base polymer having a Mw of 15,000-100,000, (b)45-60 wt % of one or more structural diluents, (c) 30-40 wt % of one ormore radical addition diluents, (d) 0.01-2.0 wt % of one or moreexternal catalysts, (e) 0.01-10 wt % photoinitiators, (f) 0-10 wt % ofone or more photosensitizers, and (g) 0-10 wt % stabilizer/process aid.

An additional embodiment of the present subject matter includes a curein place liquid comprising: (a) 5-70 wt % of a bodying componentcomprising a non-acrylic base polymer having a Mw of 1,000 to 500,000,in certain embodiments 1,000-100,000, and in still other embodiments1,000-50,000, selected from the group consisting of polyolefins,polyvinyl aromatics, polyurethanes, polycarbonates, polyesters,polyethers, and combinations thereof, (b) 5-80 wt % of one or morestructural diluents, (c) 0-40 wt % of one or more radical additiondiluents, (d) 0-5.0 wt % of one or more external catalysts, (e) 0-10 wt% of one or more photoinitiators, (f) 0-10 wt % of one or morephotosensitizers, and (g) 0-10 wt % stabilizer/process aid.

An additional embodiment of the present subject matter includes a curein place liquid comprising: (a) 5-50 wt % of a bodying componentcomprising a non-acrylic polymer having a Mw of 5,000 to 1,000,000, andin certain embodiments 15,000-100,000, (b) 50-95 wt % of one or morestructural diluents, (c) 0.01-10 wt % of one or more external catalysts,and (d) 0-10 wt % stabilizer/process aid. The non-acrylic polymer isselected from the group consisting of polyolefins, polyvinyl aromatics,polyurethanes, polycarbonates, polyesters, polyethers, and combinationsthereof.

An additional embodiment of the present subject matter includes a curein place liquid comprising: (a) 5-70 wt % of a bodying componentcomprising a non-acrylic base polymer having a Mw of 1,000 to 500,000,in certain embodiments 1,000-100,000, and in still other embodiments1,000-50,000, selected from the group consisting of polyolefins,polyvinyl aromatics, polyurethanes, polycarbonates, polyesters,polyethers, and combinations thereof, (b) 5-80 wt % of one or morestructural diluents, (c) 5-70 wt % of one or more radical additiondiluents, (d) 0-5.0 wt % of one or more external catalysts, (e) 0-10 wt% of one or more photoinitiators, (f) 0-10 wt % of one or morephotosensitizers, and (g) 0-10 wt % stabilizer/process aid.

An additional embodiment of the present subject matter includes a curein place liquid comprising: (a) 10-15 wt % of a bodying componentcomprising a non-acrylic polymer having a Mw of 1,000 to 500,000, incertain embodiments 1,000-100,000, and in still other embodiments1,000-50,000, (b) 45-60 wt % of one or more structural diluents, (c)30-40 wt % of one or more radical addition diluents, (d) 0.01-2.0 wt %of one or more external catalysts, (e) 0.01-10 wt % of one or morephotoinitiators, (f) 0-10 wt % of one or more photosensitizers, and (g)0-10 wt % stabilizer/process aid. The non-acrylic polymer is selectedfrom the group consisting of polyolefins, polyvinyl aromatics,polyurethanes, polycarbonates, polyesters, polyethers, and combinationsthereof.

An additional embodiment of the present subject matter includes a curein place liquid comprising: (a) 5-70 wt % of a bodying componentcomprising an acrylic base polymer having a Mw of 5,000 to 1,000,000, incertain embodiments 15,000-250,000, and in still other embodiments15,000-100,000, (b) 5-70 wt % of a bodying component comprising anon-acrylic base polymer having a Mw of 1,000 to 500,000, in certainembodiments 1,000-100,000, and in still other embodiments 1,000-50,000,selected from the group consisting of polyolefins, polyvinyl aromatics,polyurethanes, polycarbonates, polyesters, polyethers, and combinationsthereof, (c) 5-80 wt % of one or more structural diluents, (d) 0-40 wt %of one or more radical addition diluents, (e) 0-5.0 wt % of one or moreexternal catalysts, (f) 0-10 wt % of one or more photoinitiators, (g)0-10 wt % of one or more photosensitizers, and (h) 0-10 wt %stabilizer/process aid.

An additional embodiment of the present subject matter includes a curein place liquid comprising: (a) 5-50 wt % of a bodying componentcomprising an acrylic base polymer having a Mw of 5,000 to 1,000,000, incertain embodiments 15,000-250,000, and in still other embodiments15,000-100,000, (b) 5-50 wt % of a bodying component comprising anon-acrylic base polymer having a Mw of 1,000 to 500,000, in certainembodiments 1,000 to 50,000 selected from the group consisting ofpolyolefins, polyvinyl aromatics, polyurethanes, polycarbonates,polyesters, polyethers, and combinations thereof, (c) 50-95 wt % of oneor more structural diluents, (d) 0.01-10 wt % of one or more externalcatalysts, (e) 0-10 wt % of one or more photosensitizers, and (f) 0-10wt % stabilizer/process aid.

An additional embodiment of the present subject matter includes a curein place liquid comprising: (a) 70-80 weight percent of a bodyingcomponent comprising an acrylic copolymer having a Mw of 15,000-250,000,and in certain embodiments 18,000-70,000, (b) 15-20 wt % of one or morestructural diluents, (c) 0.01-5 wt % of one or more photoinitiators, and(d) 0-10 wt % stabilizer/process aid.

An additional embodiment of the present subject matter includes a curein place liquid comprising: (a) 5-15 wt % of a bodying componentcomprising an acrylic base polymer having a Mw of 5,000 to 1,000,000, incertain embodiments 15,000-250,000, and in still other embodiments15,000-100,000, (b) 5-15 wt % of a bodying component comprising anon-acrylic base polymer having a Mw of 1,000 to 500,000, in certainembodiments 1,000-100,000, and in still other embodiments 1,000-50,000,selected from the group consisting of polyolefins, polyvinyl aromatics,polyurethanes, polycarbonates, polyesters, polyethers, and combinationsthereof, (c) 45-60 wt % of one or more structural diluents, (d) 30-40 wt% of one or more radical addition diluents, (e) 0.01-2.0 wt % of one ormore external catalysts, (f) 0.01-10 wt % of one or morephotoinitiators, (g) 0-10 wt % of one or more photosensitizers, and (h)0-10 wt % stabilizer/process aid.

An additional embodiment of the present subject matter includes a curein place liquid. The liquid comprises (a) 5-70 wt % of a bodyingcomponent comprising a non-acrylic base polymer having a Mw of 5,000 to1,000,000, selected from the group consisting of polyolefins, polyvinylaromatics, polyurethanes, polycarbonates, polyesters, polyethers, andcombinations thereof; (b) 0-40 wt % of at least one structural diluent;(c) 30-95 wt % of at least one radical addition diluent; (d) 0-10.0 wt %of a curative; (e) 0-10 wt % photosensitizer; and (f) 0-10 wt %stabilizer.

Another embodiment of the present subject matter includes methods ofcuring pressure sensitive adhesives. Specifically, a method of curing apressure sensitive adhesive comprises providing a cure in place pressuresensitive adhesive including 20-80 wt % of a bodying componentcomprising an acrylic base polymer having a Mw of 5,000 to 1,000,000,5-50 wt % of at least one structural diluent, 10-80 wt % of at least oneradical addition diluent, 0-10.0 wt % crosslinker, 0-4.0 wt % of a firstcurative, 0.01-10 wt % of a second curative, and 0-10.0 wt %stabilizer/process aid. The method also comprises exposing or subjectingthe adhesive to a first stimulus selected from the group consisting ofradiation, heat, moisture, pressure, ultrasound, chemical exposure, andcombinations thereof.

Another embodiment of the present subject matter includes a cure inplace pressure sensitive adhesive comprising (a) 50-80 wt % of anacrylic base polymer having a Mw of 250,000-750,000; (b) 10-30 wt % ofat least one structural diluent; (c) 0-0.5 wt % of at least one metalchelate crosslinker; (d) 0-2 wt % of a curative; and (e) 0.1-10 wt %stabilizer/process aid.

As will be realized, the subject matter described herein is capable ofother and different embodiments and its several details are capable ofmodifications in various respects, all without departing from theclaimed subject matter. Accordingly, the drawings and description are tobe regarded as illustrative and not restrictive.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts a dynamic mechanical analysis of certain embodiments ofthe cure in place pressure sensitive adhesive of Example 3.

FIG. 2 depicts a generalized adhesive bonding process of the presentsubject matter.

FIG. 3 depicts a procedure for a Lap Shear Test for Example 34.

FIG. 4 depicts a procedure for a Lap Shear Test for Example 35.

FIG. 5 depicts a schematic illustration of applying a liquid to asubstrate and subsequently curing the liquid in place by exposure toactinic radiation.

FIG. 6 is a schematic flowchart depicting an adhesive bonding process inaccordance with the present subject matter.

DETAILED DESCRIPTION

In certain embodiments, the cure in place adhesives of the presentsubject matter include (i) a bodying component, which may be acrylicbased or non-acrylic based or include combinations of acrylates andnon-acrylates, (ii) one or more structural diluents, (iii) one or moreradical addition diluents, and (iv) one or more additives such as (a)crosslinkers, (b) catalysts such as thermal catalysts and basecatalysts, (c) photoinitiators including radical photoinitiators, UVradical photoinitiators and type I and II photoinitiators, (d)photosensitizers including dyes, and (e) stabilizers or process aids. Anoverview of the selections for the three main components (i)-(iii) isfound in the following Table 1.

TABLE 1 Representative Listing of Main Components of CompositionsRadical Addition Diluents Bodying Components Structural Diluents ACEEB14-24 S-21 Isostearyl acrylate EB14-15 S-28 Heptadecyl acrylateEB14-16 Epon 828 Dicyciopentadiene EB14-04 Epon 834 acrylate THFacrylate EB14-02 A-186 OXE-10 EB14-03 A-187 OXE-30 M112, carbonatepolyol EP-10 S-100 EB13-97 Desmolux D100 Phenoxy ethylacrylate EB-14-22Desmolux D200 Urethane acrylate (less EB14-28 Desmodur N3200 than 2000daltons) Acrylic macromere (less EB14-29 Desmodur N100 than 10,000daltons) V2100 EB14-33 Desmodur N3300 Cycloalphatic V2100 EB14-40 PPOoligomer (less than 5,000 daltons) PAMA EB14-41 TMPO Alkoxylated THFacrylate Urethane Acrylate (more 2,000 PEO oligomer (less than daltons)5,000 daltons) Hydroxyethyl acrylate Acrylate macromer (more than 2EHoxetane 10,000 daltons) PPO oligomer (more than 5,000 Difunctionaloxetane daltons) AS-2549 Trimethylolpropane triacrylate (TMPTA)JRL4-128A Tripropyleneglycol diacrylate (TPGDA) JRL4-128B Ethoxylated (3mol) bisphenol A diacrylate JRL4-128C Ethoxylated (3 mol)trimethylolpropane triacrylate MJZ4-87-1 (EHA-VA-MA-S100) Bisphenol Adigylcidyl ether diacrylate MW1-65 (EHA-MA-S100) MW1-69(EHA-MA-E1020-S100) MW1-91 (EHA-VA-MA) MW1-93 (EHA-VA-MA-GMA) − best =MW1-101 MW1-94 (Acrylated MW1-93)

Details of these various components are provided herein.

Bodying Components

Bodying components are broadly defined herein as having a molecularweight (Mw) of at least 25,000 Daltons. The bodying component(s) may bepresent in the compositions of the present subject matter in an amountof 10-90 wt %, in certain embodiments 20-80 wt %, and in still otherembodiments 30-70 wt %, alternately 5-70 wt %, alternately 40-60 wt %,alternately 30-50 wt %, alternately 5-15 wt %, alternately 10-15 wt %,or 80 wt %. The bodying components may be acrylic based bodyingcomponents or non-acrylic based bodying components. Combinations ofthese and potentially with other components can be used. The bodyingcomponents may have molecular weights (Mw) of 5,000 to 1,000,000, incertain embodiments 15,000-250,000, and in still other embodiments15,000-100,000, alternately 1,000 to 500,000, in certain versions1,000-100,000, and in still other versions 1,000-50,000, or alternately18,000-70,000.

In certain embodiments of the present subject matter, particular acrylicbased bodying components can be used as follows. It will be understoodthat the present subject matter includes the use of correspondingmethacrylate monomers, oligomers, or components instead of, or inaddition to, any of the noted acrylate monomers, oligomers, orcomponents.

MJZ4-87-1: Bodying Component. This bodying component is a random acryliccopolymer with a number average molecular weight (Mn) of 50 k,(polydispersity index (PDI) 3.5, random copolymer) consisting of 55 wt %2-ethylhexyl acrylate, 25 wt % vinyl acetate, 18 wt % methyl acrylate,and 2 wt % Additol™ S-100.

MW1-65: Bodying Component. This bodying component is a random acryliccopolymer with Mn of 50 k, (PDI 3.5, random copolymer) consisting of 50wt % 2-ethylhexyl acrylate, 48 wt % methyl acrylate and 2 wt % Additol™S-100.

MW1-69: Bodying Component. This bodying component is a random acryliccopolymer with Mn of 50 k, (PDI 3.5, random copolymer) consisting of44.9 wt % 2-ethylhexyl acrylate, 43.1 wt % methyl acrylate 43.1%, 10.2wt % Elvacite™ 1020 (pMMA) and 1.8 wt % Additol™ S-100.

MW1-91: Bodying Component. This bodying component is a random acryliccopolymer with Mn of 50 k, PDI 3.5, random copolymer, consisting of 56.1wt % 2-ethylhexyl acrylate, 25.5 wt % vinyl acetate, 18.4 wt % methylacrylate.

MW1-93 (best example of synthesis is MW1-101). This bodying component isa random acrylic copolymer with Mn of 50 k, PDI 3.5, random copolymerconsisting of 55 wt % 2-ethylhexyl acrylate, 25 wt % vinyl acetate, 18wt % methyl acrylate, 2 wt % glycidyl ethacrylate.

MW1-94: Bodying Component. This bodying component is an adduct ofacrylic acid and MW1-93, containing 98 wt % of MW1-93 and 2 wt %glycidyl methacrylate and a chromium (3+) catalyst.

Detailed formulations for certain bodying components presented in Table1 are set forth in the following Table 2.

TABLE 2 Detailed Formulations of Bodying Components Used In AdhesiveCompositions COMPOSITION Component Backbone Monomer 1 Monomer 2 Monomer3 Monomer 4 AS-2549 Acrylic 51% 2EHA 45% BA Kh4-67 Acrylic 25% 2EHA 72%EOEOEA Kh4-46 Acrylic 25% 2EHA 72% EOEOEA Kh4-105 Acrylic 25% 2EHA 72%EOEOEA Kh4-37 Acrylic 50% BA 50% EOEOEA EB13-84 Acrylic 79% BA 20% tBALRK3-33 Acrylic 79% BA 20% tBA LRK3-44 Acrylic 80% BA 20% tBA PP81-56Acrylic 79% BA 20% tBA PP81-67 Acrylic 80% BA 20% tBA KH4-18 Acrylic 78%BA 19% tBA 4240 PPO D2000 PPO EB14-24 Acrylate 48.22% BA 48.22% tBAEB14-15 Acrylate 90.1% Butyl Acrylate EB14-16 Acrylate 45.05% BA 45.05%tBA EB14-04 Acrylate 40% BA 40% tBA EB14-02 Acrylate 80% BMA EB14-03Acrylate 80% BA M112 carbonate EB13-97 Acrylate 80% BA EB14-22 Acrylate96.44% BA EB14-28 Acrylate 48.22% BA 48.22% tBA EB14-29 Acrylate 48.22%BA 48.22% tBA EB14-33 Acrylate 90.9% BA EB14-40 Acrylate 48.22% BA48.22% tBA EB14-41 Acrylate 48.56% BA 48.56% tBA Urethane AcrylateUrethane (Mw > 2000) Acrylate macromer Acrylate (Mw > 10000) PPOoligomer PPO (Mw > 5000) MJZ4-87-1 Acrylic 55% 2-EHA 25% vinyl acetate18% methyl acrylate 2% S-100 MW1-65 Acrylic 50% 2-EHA 48% methylacrylate 2% S-100 MW1-69 Acrylic 44.9% 2-EHA 43.1% methyl acrylate 10.2%Elvacite 1020 1.8% S-100 MW1-91 Acrylic 56.1% 2-EHA 25.5% vinyl acetate18.4% methyl acrylate MW1-93 Acrylic 55% 2-EHA 25% vinyl acetate 18%methyl acrylate 2% glycidyl methacrylate MW1-94 Acrylate 98% MW1-93 2%Acrylic Acid COMPOSITION MOLECULARWEIGHT Component FunctionalityStructure Mw Mn PDI AS-2549 4% acid random 380961 61545 6.19 Kh4-67 3%epoxy P-telechelic 60441 20043 3.02 Kh4-46 3% alcohol random 36747 133012.76 Kh4-105 3% alcohol p-telechelic n/a Kh4-37 none random 54424 173373.14 EB13-84 1% alcohol tadpole 80987 53591 1.51 LRK3-33 1% alcoholtadpole 83000 37700 2.20 LRK3-44 0.4% alcohol random 81300 42960 1.89PP81-56 1% alcohol tadpole 71000 37400 1.90 PP81-67 0.4% alcohol random63500 35240 1.80 KH4-18 1.1% alcohol random 83726 58704 1.43 4240alcohol Telechelic 4000 D2000 primary amine Telechelic 2000 EB14-243.56% alcohol P-telechelic 54300 38100 1.43 EB14-15 9.1% epoxyP-telechelic 129800 48500 2.68 EB14-16 9.1% epoxy P-telechelic 16440048500 3.39 EB14-04 20% epoxy random 44700 19700 2.27 EB14-02 20% epoxyrandom n/a EB14-03 20% epoxy random n/a M112 alcohol Telechelic EB13-9720% epoxy random 40800 12300 3.32 EB14-22 3.56% alcohol P-telechelic60700 36000 1.69 EB14-28 3.56% alcohol P-telechelic 27300 18700 1.46EB14-29 3.56% alcohol P-telechelic n/a EB14-33 9.1% epoxy P-telechelicn/a EB14-40 3.56% alcohol P-telechelic n/a EB14-41 2.88% alcoholP-telechelic n/a Urethane Acrylate (Mw > 2000) Acrylate macromer (Mw >10000) PPO oligomer (Mw > 5000) MJZ4-87-1 2% epoxy Random 50000 1750003.5 MW1-65 2% epoxy Random 50000 175000 3.5 MW1-69 1.8% epoxy random50000 175000 3.5 MW1-91 none random 50000 175000 3.5 MW1-93 2% epoxyRandom 50000 175000 3.5 MW1-94 2% acrylate random 50000 175000 3.5

Abbreviations in the preceding Table 2 include BA: butyl acrylate;2-EHA: 2-ethylhexyl acrylate; tBA: tert-butyl acrylate; EOEOEA:ethoxyethoxyethylacrylate; PPO: polypropylene oxide, BMA: butylmethacrylate.

Radical Addition Diluents

Radical addition diluents are acrylic based monomers having a molecularweight (Mw) of generally less than 25,000 and/or generally having aviscosity below 25,000 cps at 25° C. Radical addition diluents areperiodically referred to herein as reactive diluents. Radical additiondiluents are present in the compositions of the present subject matterin an amount of 10-80 wt %, in certain embodiments 50-70 wt %,alternately 10-60 wt %, alternately 5-70 wt %, alternately 0-40 wt %, instill other embodiments 30-40 wt %, or alternately 7-25 wt %. Radicaladdition diluents can include a (meth)acrylate monomer and in certainversions have an overall Mw of less than 10,000 Daltons. Examples ofuseful radical addition diluents herein include ACE, isostearylacrylate, heptadecyl acrylate, dicyclopentadiene acrylate, THF acrylate,alkoxylated THF acrylate, hydroxyethyl acrylate, phenoxy ethylacrylate,urethane acrylate (Mw<2000), OXE-10, OXE-30, S-100, V2100,Cycloaliphatic V2100, and PAMA. Many of these components are describedin greater detail herein in association with the Examples. Examples ofseveral radical addition diluents are set forth in detail below.

Alkoxylated THF acrylate, is a low viscosity monofunctional monomeravailable from Sartomer as CD-611, where n is not disclosed, and whichis shown below as formula (1):

Hydroxyethyl acrylate: This radical addition diluent is shown below asformula (2):

Phenoxyethylacrylate: This radical addition diluent is shown below asformula (3):

This low viscosity monofunctional monomer is available from Sartomer asSR339.

Tetrahydrofurfuryl acrylate (THFA or THF acrylate): This radicaladdition diluent is shown below as formula (4). This low viscositymonofunctional monomer is available from Sartomer as SR285.

Structural Diluents

Structural diluents may be present in the compositions of the presentsubject matter in an amount of 5-80 wt %, alternately 5-50 wt %, incertain embodiments 10-50 wt %, alternately 5-40 wt %, alternately 10-30wt %, alternately 20-40 wt %, alternately 65-95 wt %, alternately 75-85wt %, alternately 75-95 wt %, alternately 7-25 wt %, alternately 45-65wt %, alternately 45-60 wt %, alternately 75-85 wt %, and alternately15-20 wt %. Structural diluents are periodically referred to herein asstructural components. Various structural diluents and details aredescribed in association with the Examples herein.

Various structural diluents include the following: Trimethylolpropanetriacrylate (TMPTA). This monomer is available from Sartomer as SR351and shown below as formula (5):

Tripropyleneglycol diacrylate, available from Sartomer as SR306 andshown below as formula (6):

Ethoxylated (3 mol) bisphenol A diacrylate. This monomer is availablefrom Sartomer as SR349 where n+m=3, and is shown below as formula (7):

Ethoxylated (3 mol) trimethylolpropane triacrylate, and shown below asformula (8):

This monomer is available from Sartomer as SR454.

Bisphenol A diglycidyl ether diacrylate is shown below as formula (9):

This monomer is available from Cytec as Ebecryl 600.

Radical structural components include one or more curable materialsincluding a homopolymer having a Tg>0° C. Such suitable componentsinclude trimethylolpropane triacrylate (TMPTA), ethoxylated (x mol)bisphenol A diacrylate, ethoxylated (x mol) trimethylolpropanetriacrylate, and bisphenol A digylcidyl ether diacrylate. The value x isfrom 1 to 10, in certain embodiments from 1 to 5, and in still otherembodiments 3.

Ring opening structural components can also be used in certainembodiments. Suitable ring opening structural components include S-21,S-28, Epon 828, Epon 834, Silquest® A-186 and Silquest® A-187. Alsouseful are epoxies, oxetanes, anhydrides, and lactams.

Cationically polymerizable monomers include epoxy-containing materials,alkyl vinyl ethers, cyclic ethers, styrene, divinyl benzene, vinyltoluene, N-vinyl compounds, 1-alkyl olefins (alpha-olefins), lactams andcyclic acetals.

Epoxy-containing materials that can be cured or polymerized by thecatalyst system of this subject matter are those known to undergocationic polymerization and include 1,2-, 1,3-, and 1,4-cyclic ethers(also designated as 1,2-, 1,3-, and 1,4-epoxides). The 1,2-cyclic ethersare useful in certain versions of the present subject matter.

Cyclic ethers that can be polymerized in accordance with this subjectmatter include those described in Frisch and Reegan, Ring-OpeningPolymerizations, Vol. 2 (1969). Suitable 1,2-cyclic ethers are themonomeric and polymeric types of epoxides. They can be aliphatic,cycloaliphatic, aromatic, or heterocyclic and will typically have anepoxy equivalence of from 1 to 6, and in certain embodiments 1 to 3.Particularly useful are the aliphatic, cycloaliphatic, and glycidylether type 1,2-epoxides such as propylene oxide, epichlorohydrin,styrene oxide, vinylcyclohexene oxide, vinylcyclohexene dioxide,glycidol, butadiene oxide, diglycidyl ether of bisphenol A, cyclohexeneoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate,3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate,bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, dicyclopentadienedioxide, epoxidized polybutadiene, 1,4-butanediol diglycidyl ether,polyglycidyl ether of phenolformaldehyde resole or novolak resin,resorcinol diglycidyl ether, and epoxy silicones, e.g.,dimethylsiloxanes having cycloaliphatic epoxide or glycidyl ethergroups.

A wide variety of commercial epoxy resins are available and listed inLee and Neville, Handbook of Epoxy Resins, (1967) and in P. Bruins,Epoxy Resin Technology, (1968). Representative of the 1,3- and1,4-cyclic ethers which can be polymerized in accordance with thissubject matter are oxetane, 3,3-bis(chloromethyl)oxetane, andtetrahydrofuran.

In particular, cyclic ethers which are readily available includepropylene oxide, oxetane, epichlorohydrin, tetrahydrofuran, styreneoxide, cyclohexene oxide, vinylcyclohexene oxide, glycidol, octyleneoxide, phenyl glycidyl ether, 1,2-butane oxide, diglycidyl ether ofbisphenol A (e.g., Epon 828 and DER 331), vinylcyclohexene dioxide(e.g., ERL-4206),3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (e.g.,ERL-4221),3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate(e.g. ERL-4201), bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate (e.g.,ERL-4299), aliphatic epoxy modified with polypropylene glycol (e.g.,ERL-4050 and ERL-4052), dipentene dioxide (e.g., ERL-4269), epoxidizedpolybutadiene (e.g., Oxiron 2001), silicone epoxy (e.g., Syl-Kem 90),1,4-butanediol diglycidyl ether (e.g., Araldite RD-2), polyglycidylether of phenolformaldehyde novolak (e.g., DER-431), Epi-Rez 521 andDER-438), resorcinol diglycidyl ether (e.g., Kopoxite), polyglycoldiepoxide (e.g., DER-736), polyacrylate epoxide (e.g., Epocryl U-14),urethane modified epoxide (e.g., QX3599), polyfunctional flexibleepoxides (e.g., Flexibilizer 151), and mixtures thereof as well asmixtures thereof with co-curatives, curing agents or hardeners whichalso are known (see Lee and Neville and Bruins, supra). Representativeof the co-curatives of hardeners that can be used are acid anhydridessuch as nadic methyl anhydride, cyclopentanetetracarboxylic dianhydride,pyromellitic anhydride, cis-1,2-cyclohexanedicarboxylic anhydride, andmixtures thereof.

Cationically-polymerizable monomers useful in the present subject matterinclude but are not limited to epoxy-containing materials, alkyl vinylethers, cyclic ethers, styrene, divinyl benzene, vinyl toluene, N-vinylcompounds, cyanate esters, 1-alkenes (alpha olefins), lactams and cyclicacetals.

Additional cationically-polymerizable monomers are described in U.S.Pat. No. 5,252,694 at col. 4, line 30 through col. 5, line 34.Particular monomers of this class include EPON® 828, and EPON® 1001F andthe ERL series of cycloaliphatic epoxy monomers such as ERL-4221® orERL-4206®. Particularly useful monomers are the ERL series because oftheir lower cure temperatures.

Certain lactones may be useful in the present subject matter. Thelactones which can used as comonomers in the present subject matterinclude those shown below with formulas (10)-(12):

wherein n is 4 or 5, h, i, k, and m are independently 1 or 2 and each Ris independently chosen from H or hydrocarbyl containing up to 12 carbonatoms. Particular lactones are those in which R is hydrogen or methyl,and in certain embodiments particularly useful lactones aree-caprolactone, d-valerolactone, glycolide (1,4-dioxan-2,5-dione),1,5-dioxepan-2-one and 1,4-dioxan-2-one.

An additional class of diluent that may be employed in the presentsubject matter is a ring-opening monomer diluent. Such a diluent is alsonon-reactive with the other reactants under conditions of free radicalpolymerization employed and which is capable of undergoing ring openingsubsequent to formation of the acrylate polymer during the curing step.Such ring-opening diluents comprise, without limitation, lactones,lactams, cyclic ethers and cyclic siloxanes represented by the followinggeneral formulas shown below as (13)-(16):

In formulas (13)-(16), x ranges from, for example, 3 to 11, and incertain versions 3-6 alkylene groups.

U.S. Pat. No. 5,082,922 describes the use of ring-opening monomers asdiluents in the solvent-free formation of polymers from ethylenicallyunsaturated monomers. However, this patent describes a single stepreaction of the monomers together with the ring-opened diluent. Thisdiffers from the two step strategy of certain methods of the presentsubject matter which provide for the initial formation of the polymerfrom ethylenically unsaturated monomers followed by curing of thediluent in the presence of the thus-formed polymer. The noted patentprovides for use of reaction conditions such as temperatures of at least150° C. which support both reactions in a single step.

Useful ring-opening monomer diluents include but are not limited tobutyrolactone, valerolactone, caprolactone, methy-butyrolactone,butyrolactam, valerolactam, caprolactam and siloxanes.

A siloxane ring opening monomer is Siloquest® A-186, which acts as aring opening cured structural component as well as a silane functionalstructural component through silane-silane condensation reaction.Siloquest® A-186 (beta(3,4-epoxycyclohexyl) ethyltrimethoxysilane) hasthe following formula (17):

While the polymerization reaction may be carried out in the presence ofa non-reactive solvent, the reaction can advantageously occur in thesubstantial absence of a solvent. In certain embodiments, the solventwill be present in an amount of up to about 10 percent by weight, andpreferably no more than 5 percent by weight, based on the total weightof the reactants. The solvent may be removed from the product of thediluent reaction step (such as by heating). Exemplary non-reactivesolvents include ketones, alcohols, esters and hydrocarbon solvents,such as ethyl acetate, toluene and xylene.

Oxazolines, or oxzolidines, useful in the present subject matter includethose having the following formulas (18)-(19):

where R represents a branched, saturated, aliphatic hydrocarbon radicalcontaining 5 to 8 carbons. Another suitable oxazoline is shown below as(20):

where R represents a branched, saturated, aliphatic hydrocarbon radicalcontaining 5 to 8 carbons.

The oxazolidine mixtures useful herein generally have a viscosity ofless than 8,000, and in certain versions, less than 6,500 mPa·s at 23°C. and, thus, are suitable as solventless hardeners for polymerprecursors containing isocyanate groups. In combination with polymerprecursors containing isocyanate groups, they are suitable for theproduction of solventless or low solvent, one-component systems which,in turn, are suitable as binders for high quality paints, coatingcompositions or sealing compositions. These systems are generally curedafter application by exposure to atmospheric moisture. Polymerprecursors containing isocyanate groups which are suitable for theproduction of these systems include the organic polyisocyanates orisocyanate prepolymers described, e.g., U.S. Pat. No. 4,002,601.Generally the oxazolines useful herein are described in U.S. Pat. No.5,189,176.

In certain embodiments, bismaleimides can be used. The bismaleimidesthat may be used in the present subject matter are organic compoundscontaining two maleimide groups and are prepared generally from maleicanhydride and diamines. Bismaleimides may be described by the generalformula of (21) as follows:

wherein R³ is a divalent aromatic or alicyclic organic group. In certainversions, useful bismaleimides are derived from aromatic diamines andparticularly are those wherein R³ is a polynuclear aromatic radical.Examples of such bismaleimides include 2,2-bis(4-aminophenoxy-4-phenyl)propane bismaleimide, 4,4′-bis(3-amino phenoxy) diphenyl sulfonebismaleimide, 1,4-bis(3-aminophenyl isopropylidene) benzene bismaleimideand bis(4-aminophenyl) methane bismaleimide. The bismaleimides may beused singly or as mixtures.

It is also possible to use bismaleimides in which up to 50% of themaleimide groups have been replaced by substituted maleimide groups suchas methyl maleimides or halomaleimides or by the nadimide, methylnadimide, or isomaleimide groups. Portions of the maleimide groups mayalso be replaced by succinimide, phthalimide, or substituted succinimideand phthalimide groups.

The bismaleimide may be prepared by a number of well known methods frommaleic anhydride and diamines, and a great many are readily availablefrom commercial sources.

As previously noted, in certain aspects of the present subject matter,one or more components of the compositions such as the bodyingcomponents can be non-acrylic based bodying components. A wide array ofnon-acrylic based components can be used. Nonlimiting examples includepolyolefins, polyvinyl aromatics, polyurethanes, polycarbonates,polyesters, polyethers, and combinations of these and potentially withone or more other agents and/or components. A particular nonlimitingexample of a polyvinyl aromatic is polystyrene.

Additives

Various additives and initiators are useful with the adhesives andcompositions of the present subject matter. Periodically, the term“curative” is used herein. That term refers to an agent(s) or stimulusthat promotes or causes polymerization of the polymer(s) in the subjectcomposition. Thus, the term curative includes a single agent, a singlestimulus, multiple agents, multiple stimuli, combinations of agents,combinations of stimuli, and combinations of one or more agents with oneor more stimuli. Generally, the curative(s) is activable, i.e.,activatable, by at least one of radiation, heat, moisture, pressure,ultrasound, exposure to chemical agents, and combinations thereof.Typically, the term curative as used herein refers to catalysts and/orphotoinitiators. However, it will be appreciated that the term mayinclude a wide array of other agents (and stimuli).

Thermal Catalysts. The catalysts herein may be external or internal.Catalysts may be used in an amount of 0-10 wt %, 0.1-10 wt %, 0-5 wt %,0.1-5 wt %, 0-4 wt %, 0.1-4 wt %, 0-2 wt %, 0.1-2 wt %, or 0.01-2 wt %.Suitable catalysts include blocked strong acid catalysts, which arebased on acids consisting of, for example trifluoromethanesulfonic acid(triflic acid), dinonylnaphthalene sulfonic acid (DSA),dinonylnaphthalene disulfonic acid (DDSA), hexafluoro phosphate, andammonium antimony hexafluoride (a Lewis acid), and are available fromKing Industries for example as K-Pure® CXC 1615 (diethylamine salt oftrifluoromethanesulfonic acid), Nacure® 155 (a blocked acid catalystbased on DNNDSA), K-Pure® CXC 1612 (ammonium antimony hexafluoride),Nacure® Super-A218 (zinc salt of trifluoromethanesulfonic acid), K-Pure®CXC 1738 (ammonium hexafluorophosphate), and K-Pure® CXC 1614 (ammoniumtrifluoromethanesulfonic acid).

Base catalysts can be primary, secondary or tertiary amines. A suitableprimary diamine is diamino diphenyl sulfone. Other bases includeimidizoles and ketimines. Suitable imidizoles include 2-methylimidizole, 2-ethyl 4-methyl imidizole, 2-phenyl imidizole. A listing ofimidizole curatives are found in US Patent Application Publication No.2009/0194320, paragraph [0045]. A latent base curative is dicyandiamide[DICY].

Photoinitiators. Photoinitiators include radical photoinitiators and UVradical photoinitiators. Photoinitiators may be present in thecompositions of the present subject matter in amounts of 0-10 wt %,0.01-10 wt %, 2-5 wt %, or 1-3 wt %.

Radical Photoinitiators. Thermal initiators include t-butyl peroxy2-ethylhexanoate, t-butyl peroxy pivalate, t-amylperoxy-2-ethylhexanoate, Benzoyl Peroxide, t-amyl peroxybenzoate, t-butyl peroxyacetate, and Azo compounds sold under the trade name Vazo, such as forexample Vazo 52, Vazo 67, and Vazo 88.

UV Radical Photoinitiators. The photoinitiators which are suitable inthe present subject matter include both type I and type IIphotoinitiators.

Type I photoinitiators are defined to essentially undergo a unimolecularbond cleavage reaction upon irradiation thereby yielding free radicals.Suitable type I photoinitiators are selected from a group consisting ofbenzoin ethers, benzil ketals, alpha-dialkoxy-acetophenones,α-hydroxyalkylphenones and acyl-phosphine oxides. Suitable type Iphotoinitiators are commercially available, for example, as Esacure KIP100 from Lamberti Spa, Gallarate, Italy, or as Irgacure 651 fromCiba-Geigy, Lautertal, Germany.

In general, the type I photoinitiator compounds suitable herein areselected from a group consisting of benzoin ethers, benzil ketals,α-dialkoxy-acetophenones, α-hydroxyalkylphenones and acyl-phosphineoxides.

Type II photoinitiators are defined to essentially undergo a bimolecularreaction where the photoinitiators interact in an excited state with asecond compound acting as co-initiator, to generate free radicals.Suitable type II photoinitiators are selected from a group comprisingbenzophenones, thioxanthones and titanocenes. Suitable co-initiators arepreferably selected from a group consisting of amine functionalmonomers, oligomers or polymers whereby amino functional monomers andoligomers are used in certain embodiments. Both primary, secondary andtertiary amines can be used whereby tertiary amines are used in certainembodiments. Suitable type II photoinitiators are commerciallyavailable, for example, as Esacure TZT from Lamberti Spa, Gallarate,Italy, or as 2- or 3-methylbenzophenone from Aldrich Co., Milwaukee,Wis., USA. Suitable amine co-initiators are commercially available, forexample, as GENOMER® 5275 from Rahn AG, Zurich, Switzerland.

Specific examples of type II photoinitiator compounds includebenzophenones and thioxanthones. In a particular embodiment,co-initiator compounds such as amines may be present and may interactwith the type II photoinitiator compounds.

Crosslinkers. The crosslinkers useful herein include radiationactivatable crosslinking agents, which are selected from the groupconsisting of aldehydes, ketones, quinones, thioxanthones, ands-triazines. Metal chelate crosslinker catalysts are also envisioned.The crosslinkers may be present in the compositions of the presentsubject matter in an amount of 2 to 95 wt %, 0-4 wt %, 0.01-4 wt %,0.01-2 wt %, 0-2 wt %, 0.01-1 wt %, 0-1 wt %, 0.01-0.5 wt %, or 0-0.5 wt%.

Photosensitizers. Each sensitizer tends to have its own characteristicresponse in the visible and ultraviolet light spectrum, so they may beused in combination to broaden the light response and/or increase thespeed of response to exposure to light.

Photosensitizers may be used in the compositions of the subject matterin amounts such as 0-15 wt %, 0-01-15 wt %, 0-10 wt %, 0.01-10 wt %, 0-5wt %, 0.01-5 wt %, 0-2 wt %, 0.01-2 wt %, 0-1 wt, and 0.01-1 wt %.Photosensitizers may be sensitizing dyes.

Illustrative sensitizing dyes are those in the following categories:diphenylmethane, xanthene, acridine, methine and polymethine, thiazole,thiazine, azine, aminoketone, porphyrin, colored aromatic polycyclichydrocarbons, thioxanthenones p-substituted aminostyryl compounds andaminotriaryl methanes.

Stabilizers and Processing Aids. Several categories of stabilizers andprocessing aids are envisioned, including oils/waxes, antioxidants,photosensitizers, rheology modifiers, fillers, radical structuralcomponents, ring opening structural components, epoxies, oxetanes,anhydrides, lactams, lactones, oxazolines, isocyanates, bismaleimides,and azodioxides. Stabilizers and process aids are used in thecompositions of the subject matter in amounts such as 0-10 wt %, 0.1-10wt %, 0-4 wt %, 0.1-4 wt %, 0-3 wt % and 0.1-3 wt %. In certainembodiments, it may be useful to utilize an azodioxide as a stabilizer.An example of such is the stabilizer commercially available fromHampford Research, Inc. of Stratford, Conn., under the designationUVTS-52. UVTS-52 is a thermally reversible azodioxide. UVTS-52 (CAS34122-40-2) is believed to be1,4,4-trimethyl-2,3-diazabicyclo-[3.2.2]-non-2-ene-2,3-dioxide.

Plasticizers—Oils and waxes. Suitable plasticizers include plasticizingoils, such as mineral oil, but also olefin oligomers and low molecularweight polymers, or glycol benzoates, as well as vegetable and animaloil and derivatives of such oils. The petroleum-derived oils that may beemployed are relatively high boiling temperature materials containingonly a minor proportion of aromatic hydrocarbons. In this regard, thearomatic hydrocarbons should in certain embodiments be less than 30%,and more particularly less than 15%, by weight, of the oil. Alternately,the oil may be fully non-aromatic. Suitable oligomers included asplasticizers may be polypropylenes, polybutenes, hydrogenatedpolyisoprene, hydrogenated butadiene, or the like having averagemolecular weights between about 100 and about 10,000 g/mol. Suitablevegetable and animal oils include glycerol esters of the usual fattyacids (for example, stearic, oleic, linoleic, linolenic) andpolymerization products thereof. Other plasticizers may be used providedthey have suitable compatibility. Nyflex® 222B, a naphthenic mineral oilmanufactured by Nynas Corporation, has also been found to be anappropriate plasticizer. As will be appreciated, plasticizers havetypically been employed to reduce the viscosity of the overall adhesivecomposition without substantially decreasing the adhesive strengthand/or the service temperature of the adhesive. The choice ofplasticizer can be useful in formulation for specific end uses (such aswet strength core applications). Because of economics involved inproduction and in material cost, as plasticizers are usually of lowercost than other materials involved in the formulation like polymers andtackifying resins, the amount of plasticizer in the adhesive should bemaximized for cost considerations.

Waxes in amounts of 0% to 20% by weight or 0.1-20 wt %, or 0.1-15 wt %,can also be used in the adhesive compositions, and are used to reducethe melt viscosity of the adhesives without appreciably decreasing theiradhesive bonding characteristics. These waxes also are used to reducethe open time of the composition without affecting the temperatureperformance.

Examples of useful wax materials include the following.

Low molecular weight (100-6000 g/mol) polyethylene having a hardnessvalue, as determined by ASTM method D-1321, of from about 0.1 to 120 andASTM softening points of from about 66° C. to 120° C. can possibly beused.

Petroleum waxes such as paraffin wax having a melting point of fromabout 130° F. to 170° F. and microcrystalline wax having a melting pointof from about 135° F. to 200° F., the latter melting points beingdetermined by ASTM method D 127-60 can possibly be used.

Atactic polypropylene having a Ring and Ball softening point of fromabout 120° to 160° C. can potentially be used.

Metallocene catalyzed propylene-based wax under the name “Licocene”commercialized by Clariant International, Ltd., Muttenz, Switzerland,can possibly be used.

Metallocene catalyzed wax or single-site catalyzed wax like for examplethose described in U.S. Pat. Nos. 4,914,253 and 6,319,979, and WO97/33921 and WO 98/03603 can potentially be used.

Paraffin waxes, microcrystalline waxes, polyethylene waxes,polypropylene waxes, by-product polyethylene waxes, synthetic waxes madeby polymerizing carbon monoxide and hydrogen such as Fischer-Tropschwaxes, oxidized Fischer-Tropsch waxes, functionalized waxes, andmixtures thereof, can possibly be used.

Polyolefin waxes. As used herein, the term “polyolefin wax” refers tothose polymeric or long-chain entities comprised of olefinic monomerunits. These materials are commercially available from Westlake ChemicalCo. under the trade name “Epolene.”

The materials which are used in certain embodiments of the presentsubject matter have a Ring and Ball softening point of 200° F. to 350°F. As should be understood, each of these waxes is solid at roomtemperature. Other useful substances include hydrogenated animal, fishand vegetable fats and oils such as hydrogenated tallow, lard, soy oil,cottonseed oil, castor oil, menhadin oil, cod liver oil, etc., and whichare solid at ambient temperature by virtue of their being hydrogenated,have also been found to be useful with respect to functioning as a waxmaterial equivalent. These hydrogenated materials are often referred toin the adhesives industry as “animal or vegetable waxes.”

Antioxidants. The adhesive also typically includes about 0.1% to about5% of a stabilizer or antioxidant. The stabilizers which are useful inthe adhesive compositions of the present subject matter are incorporatedto help protect the polymers noted above, and thereby the total adhesivesystem, from the effects of thermal and oxidative degradation whichnormally occurs during the manufacture and application of the adhesiveas well as in the ordinary exposure of the final product to the ambientenvironment. Such degradation is usually manifested by a deteriorationin the appearance, physical properties and performance characteristicsof the adhesive. In certain embodiments, a particularly usefulantioxidant is Irganox 1010, atetrakis(methylene(3,5-di-teri-butyl-4-hydroxyhydrocinnamate))methanemanufactured by Ciba-Geigy. Among the applicable stabilizers are highmolecular weight hindered phenols and multifunctional phenols, such assulfur and phosphorus-containing phenols. Hindered phenols are wellknown to those skilled in the art and may be characterized as phenoliccompounds which also contain sterically bulky radicals in closeproximity to the phenolic hydroxyl group thereof. In particular,tertiary butyl groups generally are substituted onto the benzene ring inat least one of the ortho positions relative to the phenolic hydroxylgroup. The presence of these sterically bulky substituted radicals inthe vicinity of the hydroxyl group serves to retard its stretchingfrequency and correspondingly, its reactivity. This steric hindrancethus provides the phenolic compound with its stabilizing properties.Representative hindered phenols include:

-   -   1,3,5-trimemyl-2,4,6-tris(3-5-di-tert-butyl-4-hydroxybenzyl)benzene;    -   pentaerythritol tetrakis-3(3,5-di-tert-butyl-4-hydroxyphenyl)        propionate;    -   n-octadecyl-3(3,5-ditert-butyl-4-hydroxyphenyl) propionate;    -   4,4′-methylenebis(4-methyl-6-tert butylphenol);    -   4,4′-thiobis(6-tert-butyl-o-cresol);    -   2,6-di-tert-butylphenol;    -   6-(4-hydroxyphenoxy)-2,4-bis(n-ocytlthio)-1,3,5-triazine;    -   2,4,6-tris(4-hydroxy-3,5-di-tert-butyl-phenoxy)-1,3,5-triazine;    -   di-n-octadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate;    -   2-(n-octylthio)ethyl-3,5-di-tert-butyl-4-hydroxybenzoate; and    -   sorbitol hexa-(3,3,5-di-tert-butyl-4-hydroxy-phenyl) propionate.

The performance of these stabilizers may be further enhanced byutilizing, in conjunction therewith; (1) synergists such as, forexample, as thiodipropionate esters and phosphites; and (2) chelatingagents and metal deactivators as, for example,ethylenediaminetetraacetic acid, salts thereof, anddisalicylalpropylenediimine.

Ultraviolet Inhibitors. Antioxidants may be used to retard the oxidativeattack on the adhesive composition, which can result in loss of theadhesive and cohesive strength of adhesive composition. Usefulantioxidants include but are not limited to amines, such asN—N′-di-beta-naphthyl-1,4-phenylenediamine, available as AGERITE D,phenolics, such as 2,5-di-(t-amyl) hydroquinone, available as SANTOVARA, from Monsanto Chemical Co., tetrakis[ethylene3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propianate]methane, available asIRGANOX 1010 from Ciba-Geigy Corp., and2-2′-methylenebis(4-methyl-6-tert butyl phenol), available asANTIOXIDANT 2246, and dithiocarbamates, such as zinc dithiodibutylcarbamate.

Rheology Modifiers. Rheology modifiers can be added to change thethixotropic properties of the composition. Suitable rheology modifiersinclude polyamide waxes, fumed silica, flow control additives, reactivediluents, anti-settling agents, alpha-olefins, hydroxyl-terminatedsilicone-organic copolymers, including but not limited tohydroxyl-terminated polypropyleneoxide-dimethylsiloxane copolymers, andcombinations thereof.

Fillers. Fillers can be used to impart strength or reduce overall cost.Useful fillers herein include aluminum trihydroxide, calcium hydroxide,expandable microspheres sold under the trade name Expancel®, carbonblack, titanium dioxide or nickel coated glass spheres.

In certain versions of the present subject matter, a filler, rheologymodifier and/or pigment is present in the adhesive. These can performseveral functions, such as modifying the rheology of the adhesive in adesirable way, absorbing moisture or oils from the adhesive or from asubstrate to which it is applied, and/or promoting cohesive, rather thanadhesive, failure. Other examples of such materials include calciumcarbonate, calcium oxide, talc, coal tar, textile fibers, glassparticles or fibers, aramid pulp, boron fibers, carbon fibers, mineralsilicates, mica, powdered quartz, bentonite, wollastonite, kaolin, fumedsilica, silica aerogel or metal powders such as aluminum powder or ironpowder. Among these, calcium carbonate, talc, calcium oxide, fumedsilica and wollastonite are particularly useful, either singly or insome combination, as these often promote the desired cohesive failuremode.

In addition to the various particular compositions described herein, thepresent subject matter also provides several additional specificcompositions as set forth below. It will be appreciated that these arerepresentative, non-limiting examples of other particular compositionsof the present subject matter.

An additional embodiment of the present subject matter includes a curein place pressure sensitive adhesive comprising: (a) 50-80 wt % of anacrylic base polymer having a Mw of 250,000-750,000, (b) 20-40 wt % ofone or more structural diluents, (c) 0-30 wt % of an optionalacrylic-epoxy functional component, (d) 0-0.5 wt % of a metal chelatecrosslinker, and (e) 0-2 wt % of one or more external catalysts.

Another embodiment of the present subject matter is a curable pressuresensitive adhesive formed from a blend, wherein the blend comprises (a)a high-molecular weight (for example 400-600 k g/mol) random copolymerincluding (i) an alkyl acrylate base monomer; (ii) vinyl acetate; (iii)methyl acrylate; (iv) acrylic acid; and (v) a silane crosslinkingmonomer; (b) a low molecular weight (for example 20-50 k g/mol) randomcopolymer including (i) a linear alkyl acrylate base monomer, (ii) abranched alkyl acrylate base monomer and (iii) an epoxy functionalmethacrylate monomer; (c) an oligomer such as STPE-30 from Wacker; (d)an acrylate-glycidyl ester of a 10-carbon carboxylic acid; (e) acationic reactive diluent such as trimethylolpropane oxetane (TMPO); (f)high molecular weight acid functional acrylic diluent monomer, (exampleof which is 2-acryloyloxypropyl phthalate); (g) bisphenol-A based epoxyresin that is semi-solid at room temperature; and (h) a crosslinker andsilane catalyst such as aluminum acetylacetonate.

The present subject matter also provides methods and techniques forbonding using the liquids and compositions described herein. FIG. 2schematically depicts an adhesive bonding process 300 according to thepresent subject matter. In process 300, a layer or coating 310 ofcomposition as described herein is applied to a substrate or film ofinterest 320. The composition can be applied in a wide variety oftechniques such as by spraying or coating, generally depicted atoperation 330. The coated or otherwise applied composition is thenrendered tacky by exposure to UV radiation for example, shown as 340 inFIG. 2. At this state, the composition is typically referred to as“A-stage” and in certain embodiments may exhibit a T-peel value of 0.17lbs. and a 180° peel of 0.64 lbs. Another material layer such as alaminate of copper and aluminum foil shown as 350 is then contacted withthe tacky A-stage composition 310. The resulting layered assembly isdirected to one or more processing stations such as a laser patterningstation 360 which forms a patterned laminate depicted as 370 in FIG. 2.Depending upon the end use requirements, additional processing such asremoval of a strip foil matrix can be performed such as at operation 375at which a waste matrix 380 is collected. The resulting processedlaminate is shown as 385. The processed laminate 385 may then besubjected to one or more additional processing operations such as athermal cure, shown as 390. After thermal curing, the composition 310referred to as “B-stage” typically exhibits significantly greater T-peeland 180° peel values as compared to those of its A-stage. For example,B-stage T-peel values can be about 0.37 lbs. and 180° peel values can beabout 3.6 lbs. The cured product can be collected in roll form or sheetform, 395.

Generally, in various embodiments of the present subject matter theliquids or compositions described herein can be rendered tacky orexhibit properties typically associated with pressure sensitiveadhesives upon at least partially curing the composition by any of theagents or stimuli as described herein. In certain versions, this firstcure or partial cure is achieved by exposing the composition to UVradiation, electron beam, heat, or combinations of these. Furthermore,the partially cured composition can then be further cured by exposure toheat, chemical agents including water or moisture, pressure, orcombinations thereof.

The present subject matter compositions can be used in a wide array ofapplications. For example, an application of particular use couldinvolve foamed articles made from the compositions described herein. Oneor more conventional blowing agents could be incorporated in thecompositions of the present subject matter, blowing or expansioneffected, to thereby produce a foamed layer or article. The compositionscould also be used to adhesively bond foamed articles to other surfaces,substrates, or items.

More specifically, the present subject matter can be used for bonding orotherwise adhering film to film, film to foil, aprons to foil, aprons tofilm, fabric to fabric, fabric to nearly any other material or substratesuch as films, papers, and metals, paper to metal, metal to metal, filmsto other plastics, plastics to plastics, and combinations of these withother surfaces, materials, and/or substrates. The present subject mattercan also be used to provide chemical resistance, e.g., corrosionresistance, to a variety of surfaces and substrates. For example, thesubject matter can be used to provide chemically resistant labels, andsolvent resistant laminates such as solvent resistant glass and foilassemblies. The present subject matter can also be utilized to form filmlaminates such as film to film laminates. Another contemplatedapplication of the present subject matter is in the field of shrinksleeves and shrink sleeve labels. Furthermore, the present subjectmatter may find wide applications for solvent welding of two films. Yetanother field of application relates to corrosion protection ofcomponents and particularly metal pipes such as oil and gas pipelines.The present subject matter compositions and methods can be used toprovide or increase impact resistance, structural integrity, andprotection against corrosion or exposure to environmental agents. Aparticular and nonlimiting example of such corrosion protection isproviding an outer layer, an inner layer, or both along outer and/orinner circumferential surfaces of pipes. Another significant benefit ofcertain compositions in accordance with the present subject matter isthat the compositions can be subjected to bending, flexing, or otherstresses without cracking. This is desirable if for example thecomposition(s) is applied to piping. Yet another contemplatedapplication for certain compositions of the present subject matter is informing fiberglass structures such as marine boat hulls, certainsporting goods, and structural members. Still another application forthe present subject matter is in “roll on, shrink on” (ROSO)applications.

EXAMPLES Examples 1-4

The cure in place adhesives of certain embodiments of the presentsubject matter can be described as an acrylic polymer admixed withreactive diluents, oligomers, and structural components. Additionaldetails of the present subject matter are provided in the followingexamples.

Example 1 High Performance PSA with Moisture Curable Oligomer (Cure inPlace Adhesive)

Example 1 is an acrylic polymer with a latent reactive oligomer(STPE-30). The STPE-30 oligomer cures by a silane-silane condensationreaction. Optionally, the base polymer as well may have silanefunctionality and can co-react with the reactive oligomer.

Example 2 High Performance PSA with UV Curable Oligomer (Cure in PlaceAdhesive)

Example 2 is an acrylic polymer admixed with reactive diluents andstructural components triggered by UV exposure to transform the adhesivefrom liquid to a solid PSA, and cured to full strength by heating duringfilm to film lamination.

In order to incorporate an in-situ moisture cure into a high performancepressure sensitive adhesive system, an acrylic polymer, tackifer, andreactive oligomer are admixed in solvent. This system is coated intotape form under conditions which leaves a portion of the oligomer latentto react after application and exposure to humidity as described herein.

Example 3 High Performance PSA with Moisture Curable Oligomer (Cure inPlace Adhesive, Solid Components)

The composition of Example 3 is a high performance PSA with moisturecurable oligomer (Cure In Place Adhesive). In order to incorporate thein-situ moisture cure into a high performance pressure sensitiveadhesive system, an acrylic polymer, tackifer, and reactive oligomer areadmixed or otherwise combined in solvent. This system is coated intotape form under conditions which leaves a portion of the oligomer latentto react after application and exposure to humidity.

TABLE 3 Formulation of Example 3 PSA Weight Percent Component 54.45%  DEV-8631U (acrylic base polymer) 25% Terpene phenolic tackifier(softening point 110-120° C.) 20% Terpene phenolic tackifier (softeningpoint 110-120° C.) 0.55%   Metal chelate aluminum acetyl acetonate(crosslinker &catalyst)

The acrylic base polymer is a high molecular weight (400-600 k g/mol)random copolymer including (a) an alkyl acrylate base monomer; (b) vinylacetate; (c) methyl acrylate; (d) acrylic acid; and (e) a silanecrosslinking monomer.

An example of the acrylic base polymer is DEV8631U, which is a randomcopolymer having a molecular weight (Mw) of about 518,000 g/mol, whichincludes the following constituents.

TABLE 4 Acrylic Base Polymer (i.e., DEV8631U) in Example 3 PSA WeightComponent Percent 2-Ethylhexyl acrylate (base monomer) 57.95 Vinylacetate (modifying monomer) 25 Methyl acrylate 15 Acrylic acid (high Tgmonomer, crosslinking site) 3 methacroyloxypropyltrimetoxy silane(crosslinking monomer) 0.05

The reactive oligomer is a silane-terminated polyether (an oligomer)such as STPE-30 from Wacker as shown below as formula (22). STPE-30 is asilane terminated polyether. The two silane-terminated polypropyleneglycols shown are based on the same polyether. The difference is in theend group.

The crosslinker and catalyst is aluminum acetylacetonate and is shownbelow as formula (23):

The adhesive bonding process is depicted in FIG. 6. Referring to FIG. 6,generally, a bonding process 200 in accordance with the present subjectmatter is as follows. In operation 210, a composition as describedherein is coated or otherwise applied onto a film or substrate. Anexample of such a film is a release film. After appropriate application,the composition is dried which typically also includes removal of atleast a portion of any solvent in the composition, as depicted asoperation 220. Representative conditions for drying include exposure to80° C. for about 5 minutes. In operation 230, the composition is thencured in place by exposure to heat and/or humidity, to thereby form ahigh strength adhesive, 240. The condensation reaction taking place isshown below:˜Si—OCH₃+H₂O→˜Si—O—Si˜+CH₃OH

FIG. 1 depicts a dynamic mechanical analysis of the cure in placepressure sensitive adhesive of Example 3.

Example 4 Liquid Composition Curable to PSA (UV) and B-Staged DuringFilm to Film Lamination (Cure in Place Adhesive)

In Example 4, an acrylic polymer is admixed with reactive additiondiluents and structural diluents.

TABLE 5 Formulation of Example 4 Liquid Composition Weight PercentComponent 15% ACE monomer stage components (reactive diluent) 10% V2100(reactive diluent) 10% Epon 834 (structural component)  9% TMPO Oxetane(structural component) 56% EB14-04 (acrylic polymer)

An example of the reactive diluent is ACE monomer ACE™ hydroxyl acrylatemonomer, provided by Momentive Performance Materials, LeverkusenGermany, which is the reaction product of acrylic acid with Cardura™.Cardura is the glycidyl ester of Versatic™ Acid 10, a highly branchedsaturated carboxylic acid containing 10 carbon atoms. ACE has a uniquestructure combining a bulky hydrophobic tail, a pendant hydroxyl groupand an acrylate functionality, with a molecular weight about 300. ACEhas the structure shown below as formula (24):

Another reactant diluent, a high molecular weight acid functionalacrylic diluent monomer, V-2100, which is 2-acryloyloxypropyl phthalate,available from San Esters Corporation, New York, N.Y., is shown asformula (25) as follows:

A structural component is EPON™ Resin 834, which is a BPA based epoxyresin that is semi-solid at room temperature, available from MomentivePerformance Materials. Systems using EPON Resin 834 can be formulated tobe useful in a variety of high solids and tar modified coatings, hightoughness adhesives, laminating, and prepreg molding materials. Becauseof its higher molecular weight, EPON Resin 834 provides enhanced systemreactivity, surface tack and cured resin toughness in comparison toliquid grade BPA epoxies, but reduces elevated temperature performance.EPON Resin 834 is especially useful in applications requiring extrasurface tack, cure speed or toughness.

Another structural component is a cationic reactive diluent such astrimethylolpropane oxetane (TMPO). A UV/EB cationic formulation can beformed and which includes mostly resins, diluents, and photoinitiatorssuch as 3, 4, epoxy cyclohexyl methyl-3,4 epoxy cyclohexane carboxylate(shown as formula (26) below) as the main resin and TMPO as the reactivediluent:

An acrylic component is a low molecular weight (20-50 k g/mol) randomcopolymer including (a) a linear alkyl acrylate base monomer, (b) abranched alkyl acrylate base monomer and (c) an epoxy functionalmethacrylate monomer.

An example of the acrylic component is the following, which is a lowmolecular weight polymer, EB14-04, which is a random copolymer having aMw of about 40,000 g/mol:

TABLE 6 Example of Acrylic Component, i.e., EB14-04 in Example 4 LiquidComposition Weight Component percent Butyl Acrylate (Base Monomer) 40t-Butyl Acrylate 40 S-100 (cycloaliphatic epoxy functional methacrylatemonomer) 30

The adhesive bonding process is depicted in FIG. 6.

Examples 5-7

Examples 5-7 illustrate polymerization processes that can be used toform components and compositions of the present subject matter.

Example 5 Polymerization of Components with Pseudo Telechelic, ExampleHaving Epoxy Functionality Using SFRP Agent

An acrylic copolymer with reactive functionality positioned in thesegments adjacent to the polymer chain end, shown below as formula (27):

is prepared as follows. Into a 1500 ml reactor equipped with a heatingjacket, agitator, reflux condenser, feed tanks and nitrogen gas inletthere is charged 8.30 g of Blocbuilder from Arkema Inc. Monomers andsolvent are added to a feed vessel in the following amounts:

-   -   22.30 g of 2-ethyl hexyl acrylate;    -   64.30 g of ethoxy ethoxy ethyl acrylate; and    -   85.30 g of propyl acetate

The Blocbuilder in the reactor and the monomers and solvent in the feedvessel are sparged with a constant nitrogen purge for 30 minutes at roomtemperature. After the hold, the monomer and solvent mix is fed to thereactor to generate a small portion of the non-reactive segment adjacentfrom reactive polymer mode in order to add acrylate groups to theBlocbuilder. The reactor charge mixture then is heated to greater than70° C. (reactor jacket 75° C.) and held for 30 min. After the secondhold, the reactor charge mixture is cooled to room temperature(approximately 25° C.). Once the reactor charge reaches roomtemperature, 13.40 g of Synasia Epoxy S-100 is charged to the reactor.After the epoxy addition, the reactor is sealed and sparged with aconstant nitrogen purge for another 30 minutes at room temperature.After the 30 minute sparge, the reactor mix is heated to 100° C. Whilethe reactor mix heats to 100° C., 579.10 g of ethoxy ethoxy ethylacrylate and 201.10 g of 2-ethyl hexyl acrylate are charged to the feedvessel and sparged with a constant nitrogen purge. When the reactor mixreaches 100° C., time is set to zero (T=0). At T=15 minutes, a sample istaken for Gas Chromatography Analysis to check for monomer conversion.After monomer conversion is confirmed (approximately 30 minutes, T=45),the reactor mix is held under reflux at a temperature between 110° C.and 117° C. until the epoxy is >90% converted (approximately 70% 2-EHAand EOEOEA conversion). At this conversion, the reagent feed mixturewith an active nitrogen purge is added over a period of 180 minutes tothe reactor. During the reagent feed the temperature of the reaction isheld under reflux at 110-118° C. The reaction conditions are maintainedafter completion of the reagent feed until a conversion of 80% of 2-EHAand EOEOEA is achieved. This is to create the remainder of thenon-reactive segment adjacent to the function end segment. At thisconversion, 13.40 g of Synasia Epoxy S-100 and 13.40 g of propyl acetateare rapidly fed to the reactor (approximately 2 min.) to create thefinal functional end segment. The reaction conditions are maintaineduntil a conversion of 2-EHA and EOEOEA greater than 98% is achieved. Theresulting solution polymer is then cooled to ambient temperature anddischarged from the reactor. The total theoretical Mn of the polymer is41,000 g/mol. The non-reactive middle segment is 32,000 g/mol and thefunctional end segments are 4,500 g/mol each.

The measured molecular weight (Mn) of the total acrylic polymer is20,043 g/mol (determined by gel permeation chromatography relative topolystyrene standards) and the polydispersity is 3.02. The calculated Mwis therefore 60,530 g/mole.

Example 6 Polymerization with Single Functional End Segment (Tadpole),Example Having Alcohol Functionality Using SFRP Agent

An acrylic copolymer with reactive functionality positioned in thesegment adjacent to the polymer chain end, shown as (28):

is prepared as follows. Into a 1500 ml reactor equipped with a heatingjacket, agitator, reflux condenser, feed tanks and nitrogen gas inletthere is charged 11.41 g of Blocbuilder. Monomers are added to a feedvessel in the following amounts:

-   -   105.93 g of n-butyl acrylate;    -   26.48 g of tert. butyl acrylate; and    -   17.26 g of 4-hydroxy propyl acrylate

The Blocbuilder in the reactor and the monomers and solvent in the feedvessel are sparged with a constant nitrogen purge for 30 minutes at roomtemperature. After the hold, the monomer and solvent mix is fed to thereactor to generate a small portion of the reactive segment adjacentfrom reactive polymer mode in order to add acrylate groups theBlocbuilder. The reactor charge mixture then is heated to greater than70° C. (reactor jacket 75° C.) and held for 30 min. After the secondhold, the reactor mix is heated to 100° C. While the reactor mix heatsto 100° C., 1071.14 g of butyl acrylate and 267.78 g of tert-butylacrylate are charged to the feed vessel and sparged with a constantnitrogen purge. When the reactor mix reaches 100° C., a timer is set tozero (T=0) and held between 100 and 105° C. At T=15 minutes, a sample istaken for Gas Chromatography Analysis to check for monomer conversion.After monomer conversion is confirmed (approximately 30 minutes, T=45),the reactor mix is held at a temperature between 100° C. and 105° C.until >80% converted butyl acrylate. At this conversion, the reagentfeed mixture with an active nitrogen purge is added over a period of 180minutes to the reactor. During the reagent feed the temperature of thereaction is held between at 100-105° C. The reaction conditions aremaintained after completion of the reagent feed until a butyl acrylateconversion greater than 98% is achieved. The resulting polymer is thencooled to ambient temperature and discharged from the reactor. The totaltheoretical Mn of the polymer is 50,000 g/mol. The non-reactive segmentis 45,000 g/mol and the functional end segment is 5,000 g/mol each.

The measured molecular weight (Mn) of the total acrylic polymer is53,591 g/mol (determined by gel permeation chromatography relative topolystyrene standards) and the polydispersity is 1.51. The calculated Mwis therefore 80,922.

Example 7 Random Functional Distribution Example Having AlcoholFunctionality

An acrylic copolymer with reactive functionality positioned randomlythroughout the polymer chain, as generally shown below as (29):

is prepared as follows. Into a 1500 ml reactor equipped with a heatingjacket, agitator, reflux condenser, feed tanks and nitrogen gas inletthere is charged 139.37 g of toluene. Monomers are added to a feedvessel in the following amounts:

-   -   83.16 g of 2-ethyl hexyl acrylate;    -   239.51 g of ethoxy ethoxy ethyl acrylate; and    -   9.98 g of 4-hydroxy propyl acrylate

To a second feed vessel, solvent and initiator are added in thefollowing amounts:

-   -   3.33 g of lauryl peroxide; and    -   30.00 g of toluene

The toluene in the reactor, initiator mix, and the monomers in the feedvessel are sparged with a constant nitrogen purge for 30 minutes at roomtemperature. After the hold, the toluene in the reactor is heated to105° C., in which there is a light reflux off the condenser. At thispoint, the monomer and initiator mix is fed over 90 minutes to thereactor. During the reagent and initiator feed, the reactor mix is heldat a temperature between 105° C. and 116° C. under reflux. The reactionconditions are maintained after completion of the reagent and initiatorfeed for 60 minutes. During the 60 minute hold, a cook-off catalyst feedis prepared in a feed vessel. The cook-off catalyst feed consisted of24.28 g of toluene and 0.37 g of t-Amyl peroxy pivalate. The cook-offcatalyst is sparged under a constant nitrogen purge for 15 minutes.After the 60 minute hold, the cook-off catalyst is fed over 30 minutesto the reactor. Once the cook-off catalyst feed is depleted, thereaction is maintained >110° C. for 60 minutes. The resulting solutionpolymer is then cooled to ambient temperature and discharged from thereactor.

The measured molecular weight (Mn) of the total acrylic polymer is13,301 g/mol (determined by gel permeation chromatography relative topolystyrene standards) and the polydispersity is 2.76. The calculated Mwis therefore 36,711.

Examples 8-39

Examples 8-33 are based upon an acrylic polymer mixed with reactivediluents and structural components triggered by UV exposure to transformthe adhesive from liquid to solid PSA, and cured to full strength(structural) by heat.

Examples 8-33 are set forth in Table 7.

TABLE 7 Examples 8-33 of Adhesive Compositions *Rolling *Rolling RadicalBall Tack Ball Tack Example Addition Bodying Structural Thickness (mm)A- (mm) B- CW # Diluents Components Components *IR (mils) Stage Stage(gsm) 8 29.4% 29.4% 41.2% 34 22 ACE EB13-84 828 9 29.4% 29.4% 41.2%0.5%  57 30 ACE EB13-84 828 A-186 10 29.4% 29.4% 41.2% 3% 30 28 ACEEB13-84 828 A-186 11 29.4% 29.4% 41.2% 26 24 ACE LRK3-33 828 12 29.4%29.4% 41.2% 18 22 ACE LRK3-33 828 13 29.4% 29.4% 41.2% 16 20 ACE LRK3-44828 14 29.4% 29.4% 41.2% 24 24 ACE PP81-56 828 15 29.4% 29.4% 41.2% 4024 ACE PP81-56 828 16 29.4% 29.4% 41.2% 38 24 ACE PP81-67 828 17 29.4%29.4% 41.2% 36 24 ACE PP81-67 828 18 29.4% 29.4% 41.2% 20 16 ACE KH4-18828 19 29.4% 29.4%  8% 32.3% 22 28 ACE LRK3-44 D2000 828 20 28.1% 27.2%7.3% 37.4% 12 16 ACE LRK3-44 EB230 828 21 18.2%   8% 73.8% 138 10 ACEKH4-37 828 22 37.7%  12% 50.2% 60 28 5 >180 122 ACE KH4-37 828 23 17.5% 12% 70.5% 56 24 ACE KH4-37 828 24 17.6%  12% 70.5% 160 22 ACE KH4-46828 25 17.6%  12% 70.5% 3% 160 24 ACE KH4-46 828 A-186 26 16.5% 16.5%67.1% 30 15 ACE KH4-37 828 27 16.8%  16% 67.1% 1.5%  24 14 ACE KH4-37828 A-186 28 16.4%  18% 65.6% 52 14 ACE KH4-46 828 29 14.1% 29.4% 56.5%40 24 ACE KH4-46 828 30 29.4% 29.4% 41.2% 22 24 ACE KH4-46 828 31 29.4%29.4% 41.2% 3% 26 26 ACE KH4-46 828 A-186 32 29.4% 29.4% 41.2% 42 26 ACEKH4-37 828 33 29.4% 29.4% 41.2% 3% 30 24 ACE KH4-37 828 A-186

In Table 7, IR refers to Impact Resistance, determined in accordancewith ASTM-G14-04(2010). Rolling Ball Tack is determined in accordancewith ASTM-D3121-06.

Examples 34-36 illustrate lap shear and Rolling Ball Tack measurementsfor additional adhesive compositions of the present subject matter.

Example 34 is an acrylic polymer mixed with structural components anddried via mild heat to a PSA, and then full cure triggered by higherheat to produce a structural bond between two substrates.

Example 35 is an acrylic polymer mixed with both a reactive oligomer andstructural components and dried via mild heat to a PSA, and then fullcure triggered by higher heat to produce a structural bond between twosubstrates.

Example 36 is an acrylic polymer mixed with reactive diluents andstructural components triggered by low heat exposure to transform theadhesive from liquid to PSA, and cured to full strength (structural) byhigher heat.

Example 34:AS-2549 acrylic PSA is crosslinked with AAA and mixed withSynasia S-21 epoxy and dried mildly at 90° C. for 10 min to cast asolvent free PSA film. The initiator for thermal cure of the epoxy ismostly at temperatures less than inactive 95° C. After drying the filmto produce a PSA tape, the tape may be applied to given substrates thatare desired to be bonded. Once the tape is applied, additional heat isapplied to initiate the adhesive to transform to full strength. Thestructural bond is created at 140° C. for 15 minutes. A depiction of theLap Shear Test for Example 34 is shown in FIG. 3. The procedure is asfollows:

Lap Shear Data (Al to Al) for Example 34 is presented in Table 8.

TABLE 8 Lap Shear Data 15 MIN DWELL A STAGE PEAK LOAD (lbf) Avg. MODULUS(psi) ADDITIVE % BOS Value % Change Avg. Value % Change 100% S-21 3028.65 −59% 2.25E+06 −44% 100% S-21 40 35.75 −48% 3.36E+06 −16% PSAControl 69.25 — 4.02E+06 — 100% S-21 30 373.25 439% 1.65E+07 310% 100%S-21 40 349.95 405% 1.57E+07 292% PSA Control 69.25 69.25 — 4.02E+06 —

Lap Shear is determined as follows. ASTM D-1002 Standard Test Method forApparent Shear Strength of Single Lap Joint Adhesively Bonded MetalSpecimens by Tension Loading (Metal to Metal) (reference). Adhesivethickness is 0.0024 inch+/−0.0006 inch. The loading is at 1 inch/minute.Peak load is measured.

Example 35:AS-2549 acrylic PSA is crosslinked with AAA and mixed withSynasia S-21 epoxy and KH4-67 and dried mildly at 90° C. for 10 min tocast a solvent free PSA film. The initiator for thermal cure of theepoxy is mostly inactive at temperatures less than 95° C. After dryingthe film to produce a PSA tape, the tape may be applied to substratesthat are desired to be bonded. Once the tape is applied, additional heatis applied to initiate the adhesive to transform to full strength. Thestructural bond is created at 140° C. for 15 minutes. FIG. 4 depicts theprocedure for the Lap Shear Test for Example 35.

Lap Shear Data (Al to Al) for Example 35 is presented in Table 9.

TABLE 9 Lap Shear Data 15 MIN DWELL A STAGE PEAK LOAD (lbf) MODULUS(psi) Avg. Avg. % ADDITIVE % BOS Value % Change Value Change 75/25S21/KH4-67 30 46.60 −33% 3.73E+06  −7% 75/25 S21/KH4-67 40 30.10 −57%2.38E+06 −41% PSA Control 69.25 — 4.02E+06 — 75/25 S21/KH4-67 30 229.45231% 1.37E+07 241% 75/25 S21/KH4-67 40 348.05 403% 1.49E+07 271% PSAControl 69.25 69.25 — 4.02E+06 —

Example 36:KH4-105 an acrylic oligomer is mixed with EPON 828 epoxy,TMPO and Siloquest A-187. It is cured mildly at 110° C. for 7 min tocast a PSA film. The initiator for thermal cure of the epoxy is veryslow at temperatures less than 110° C. After drying the film to producea PSA tape, the tape may be applied to substrates that are desired to bebonded. Once the tape is applied, additional heat is applied to initiatethe adhesive to transform to full strength. The structural bond iscreated at 140° C. for 15 minutes.

Lap shear data (Al to Al) for Example 36 is presented in Table 10.

TABLE 10 Rolling Ball Tack Data for Example 36 After After 110° C. for 7min 140° C. for 15 min Rolling Ball Tack (mm) 65 (avg) >180 ASTM#D3121-06

Example 37: A liquid in accordance with the present subject matter isapplied to a substrate and subsequently cured in place by exposure toactinic radiation. An illustration is depicted in FIG. 5. Specifically,FIG. 5 schematically depicts application of a liquid or othercomposition onto a film, label, and/or container, and exposure toactinic radiation to thereby cure the liquid or composition in place. Asource of film or labels 10 having a region, face, or surface coatedwith liquid or composition 20 as described herein is provided. Incertain embodiments, one or more regions 25 or strips 30 of tackyadhesive can be provided to assist in initially securing the film orlabel to a container of interest 40. Prior to, during, and/or afterappropriate application of the film or label to the container, actinicradiation 50 is directed to the coating to thereby adhere and/or curethe coating and produce a labeled container 45. This is generallydenoted as operation A in FIG. 5. After initial application of the filmor label, wiping and/or application of heat can be performed. Additionaloperations can be performed prior to, during, and/or after operation(s)A. FIG. 5 also schematically illustrates a continuous process 100 inwhich a plurality of containers 140 receive films or labels, are exposedto actinic radiation within an enclosure 150 to thereby produce aplurality of labeled containers 145.

Table 11, below, includes exemplary formulations that representembodiments of the present subject matter. The formulations include abodying component, radical addition diluent, structural diluent andphotoinitiator and additive (i.e., Irganox® 1010) as set forth below.

TABLE 11 Exemplary Embodiments of Adhesive Compositions Bodying RadicalAddition Structural Photoinitiator Other Formulation Component DiluentDiluent % % ID ID Rel % ID Rel % ID Rel % ID Total ID Total MW1-70-1MW1-68 (MJZ4-87-1) 70 TMPO 15 S28 15 UVACure 1600 1.5 MW1-70-2 MW1-68(MJZ4-87-1) 70 TMPO 15 S28 15 Tego 1466 3 MW1-70-3 MW1-68 (MJZ4-87-1) 70TMPO 15 S28 15 Irgacure 250 1.5 MW1-70-4 MW1-68 (MJZ4-87-1) 50 TMPO 25S28 25 UVACure 1600 1.5 MW1-70-5 MW1-69 70 TMPO 15 S28 15 UVACure 16001.5 MW1-70-6 MW1-69 70 TMPO 15 S28 15 Tego 1466 3 MW1-70-7 MW1-69 70TMPO 15 S28 15 Irgacure 250 1.5 MW1-70-8 MW1-69 50 TMPO 25 S28 25UVACure 1600 1.5 MW1-87-1 MW1-68 (MJZ4-87-1) 70 ACE 15 SR-349 15Irgacure 500 2.5 MW1-87-2 MW1-68 (MJZ4-87-1) 30 ACE 35 SR-349 35Irgacure 500 2.5 MW1-87-3 MW1-68 (MJZ4-87-1) 70 CD611 6 SR-349 24Irgacure 500 2.5 MW1-87-4 MW1-68 (MJZ4-87-1) 30 CD611 14 SR-349 56Irgacure 500 2.5 MW1-87-5 MW1-68 (MJZ4-87-1) 70 SR-285 9 SR-349 21Irgacure 500 2.5 MW1-87-6 MW1-68 (MJZ4-87-1) 30 SR-285 21 SR-349 49Irgacure 500 2.5 MW1-95-1 MW1-94 100 None 0 None 0 Irgacure 500 2.5MW1-95-2 MW1-94 70 None 0 SR-349 30 Irgacure 500 2.5 MW1-95-3 MW1-94 70ACE 15 SR-349 15 Irgacure 500 2.5 MW1-95-4 MW1-94 70 ACE 30 None 0Irgacure 500 2.5 MW1-95-5 MW1-94 50 None 0 SR-349 50 Irgacure 500 2.5MW1-95-6 MW1-94 50 ACE 25 SR-349 25 Irgacure 500 2.5 MW1-95-7 MW1-94 50ACE 50 None 0 Irgacure 500 2.5 MW1-95-8 MW1-94 30 None 0 SR-349 70Irgacure 500 2.5 MW1-95-9 MW1-94 30 ACE 35 SR-349 35 Irgacure 500 2.5MW1 -95-10 MW1-94 30 ACE 70 None 0 Irgacure 500 2.5 MW1-96-1 MW1-91 100None 0 None 0 Irgacure 500 2.5 MW1-96-2 MW1-91 70 None 0 SR-349 30Irgacure 500 2.5 MW1-96-3 MW1-91 70 ACE 15 SR-349 15 Irgacure 500 2.5MW1-96-4 MW1-91 70 ACE 30 None 0 Irgacure 500 2.5 MW1-96-5 MW1-91 50None 0 SR-349 50 Irgacure 500 2.5 MW1-96-6 MW1-91 50 ACE 25 SR-349 25Irgacure 500 2.5 MW1-96-7 MW1-91 50 ACE 50 None 0 Irgacure 500 2.5MW1-96-8 MW1-91 30 None 0 SR-349 70 Irgacure 500 2.5 MW1-96-9 MW1-91 30ACE 35 SR-349 35 Irgacure 500 2.5 MW1-96-10 MW1-91 30 ACE 70 None 0Irgacure 500 2.5 MW1-102 MW1-101 70 HEA 15 SR-349 15 Irgacure 2959 2.5MW2-C1 MW1-101 70 ACE 15 SR-349 15 Irgacure 500 5 MW2-001A MW1-101 70ACE 15 SR-349 15 Irgacure 500 5 Irganox 1010 0.1 MW2-001B MW1-101 50 ACE25 SR-349 25 Irgacure 500 5 Irganox 1010 0.1 MW2-001C MW1-101 70Phenoxyethyl 15 Ebecryl 600 15 Irgacure 2959 5 Irganox 1010 0.1 acrylateMW2-001D MW1-101 50 Phenoxyethyl 25 Ebecryl 600 25 Irgacure 2959 5Irganox 1010 0.1 acrylate MW2-001E MW1-101 70 Phenoxyethyl 6 Ebecryl 60024 Irgacure 2959 5 Irganox 1010 0.1 acrylate MW2-001F MW1-101 50Phenoxyethyl 10 Ebecryl 600 40 Irgacure 2959 5 Irganox 1010 0.1 acrylateMW2-001G MW1-101 70 Phenoxyethyl 15 TPGDA 15 Irgacure 2959 Irganox 10100.1 acrylate MW2-001H MW1-101 50 Phenoxyethyl 25 TPGDA 25 Irgacure 2959Irganox 1010 0.1 acrylate MW2-001I MW1-101 70 Phenoxyethyl 15 3EO TMPTA15 Irgacure 2959 Irganox 1010 0.1 acrylate MW2-001J MW1-101 50Phenoxyethyl 25 3EO TMPTA 25 Irgacure 2959 Irganox 1010 0.1 acrylateMW2-001K MW1-101 70 Phenoxyethyl 15 TMPTA 15 Irgacure 2959 Irganox 10100.1 acrylate MW2-001L MW1-101 50 Phenoxyethyl 25 TMPTA 25 Irgacure 2959Irganox 1010 0.1 acrylate

The following Table 12 shows selected performance data for certain ofthe formulations in Table 11.

TABLE 12 Performance Data for Selected Formulations from Table 11Formulation Units MW-1-87-1 MW1-87-2 MW1-87-3 MW1-875 Tensile StrengthReading 1 lbf 17.4 12.5 14.0 12.7 Reading 2 lbf 16.6 12.2 14.9 12.2Reading 3 lbf 16.6 12.5 12.9 10.7 Reading 4 lbf 16.0 14.7 10.7 Averagelbf 16.7 12.4 14.1 11.6 St Dev. 0.6 0.2 0.9 1.0 Cross Sect Area sq in0.0020 0.0020 0.0020 0.0020 psi 8325.0 6200.0 7062.5 5787.5 T-PeelReading 1 lbf 2.8 0.1 4.2 3.4 Reading 2 lbf 2.0 3.9 3.3 Reading 3 lbf3.0 3.7 3.0 Reading 4 lbf 4.0 3.4 Average lbf 2.6 0.1 4.0 3.3 St Dev 0.50.0 0.2 0.2

Example 38: Two additional adhesive compositions according to thepresent subject matter are set forth below in Tables 13 and 14.

TABLE 13 Adhesive Composition EXP-MW2-070-A Component Type ChemicalTradename Description Loading Example Bodying Agent PolymerPolybutylmethacrylate Elvacite 2044 Mw = 142,000  1-20% 85.29% (PBMA)(Lucite Internation) PDI Unknown Diluent Monofunctional Urethaneacrylate Genomer 1122 80-99%  9.48% Monomer CAS: 63225-53-6 (Rahn Corp)Product of hydroxyethyl acrylate with butyl isocyanate PhotoinitiatorIrgacure 2959  1-5% 4.99% (BASSF) Antioxidant Irganox 1010 0.1-1% 0.25%

TABLE 14 Adhesive Composition EXP-MW2-070-B Component Type ChemicalTradename Description Loading Example Bodying Agent PolymerPolybutylmethacrylate Elvacite 2044 Mw = 142,000  1-20% 85.29% (PBMA)(Lucite Internation) PDI Unknown Diluent Monofunctional Low viscosityCN-131B 80-99%  9.48% Monomer aromatic oligomer, (Sartomer) hydroxylfunctional Photoinitiator Irgacure 2959  1-5% 4.99% (BASSF) AntioxidantIrganox 1010 0.1-1% 0.25%

Example 39: Several additional compositions according to the presentsubject matter are set forth below in Tables 15 and 16. A particularapplication for these compositions is in “roll on, shrink on” (ROSO)labeling or related technologies.

TABLE 15 Roll On, Shrink On Compositions Bodying Radical AdditionStructural Formulation Component Diluent Diluent Photoinitiator Other IDID Rel % ID Rel % ID Rel % ID Rel % ID Rel % MW2-70-A Elvacite 2044 9.54Genomer 1122 85.91 None 0 Irgacure 2959 4.3 Irganox 1010 0.25 MWS-70-BElvacite 2044 9.54 CN-131B 85.91 None 0 Irgacure 2959 4.3 Irganox 10100.25 MW3-016 Polystyrene 9.75 CN-131 87.75 None 0 Irgacure 2959 2.5 None

TABLE 16 Roll On, Shrink On Compositions Bodying Radical AdditionStructural Formulation Component Diluent Diluent Photoinitiator Other IDID Rel % ID Rel % ID Rel % ID Rel % ID Rel % MW1-70-1 MW1-68 (MJZ4-87-1)70 TMPO 15 S28 15 UVACure 1600 1.5 MW1-70-2 MW1-68 (MJZ4-87-1) 70 TMPO15 S28 15 Tego 1466 3 MW1-70-3 MW1-68 (MJZ4-87-1) 70 TMPO 15 S28 15Irgacure 250 1.5 MW1-70-4 MW1-68 (MJZ4-87-1) 50 TMPO 25 S28 25 UVACure1600 1.5 MW1-70-5 MW1-69 70 TMPO 15 S28 15 UVACure 1600 1.5 MW1-70-6MW1-69 70 TMPO 15 S28 15 Tego 1466 3 MW1-70-7 MW1-69 70 TMPO 15 S28 15Irgacure 250 1.5 MW1-70-8 MW1-69 50 TMPO 25 S28 25 UVACure 1600 1.5MW1-87-1 MW1-68 (MJZ4-87-1) 70 ACE 15 SR-349 15 Irgacure 500 2.5MW1-87-2 MW1-68 (MJZ4-87-1) 30 ACE 35 SR-349 35 Irgacure 500 2.5MW1-87-3 MW1-68 (MJZ4-87-1) 70 CD611 6 SR-349 24 Irgacure 500 2.5MW1-87-4 MW1-68 (MJZ4-87-1) 30 CD611 14 SR-349 56 Irgacure 500 2.5MW1-87-5 MW1-68 (MJZ4-87-1) 70 SR-285 9 SR-349 21 Irgacure 500 2.5MW1-87-6 MW1-68 (MJZ4-87-1) 30 SR-285 21 SR-349 49 Irgacure 500 2.5MW1-95-1 MW1-94 100 None 0 None 0 Irgacure 500 2.5 MW1-95-2 MW1-94 70None 0 SR-349 30 Irgacure 500 2.5 MW1-95-3 MW1-94 70 ACE 15 SR-349 15Irgacure 500 2.5 MW1-95-4 MW1-94 70 ACE 30 None 0 Irgacure 500 2.5MW1-95-5 MW1-94 50 None 0 SR-349 50 Irgacure 500 2.5 MW1-95-6 MW1-94 50ACE 25 SR-349 25 Irgacure 500 2.5 MW1-95-7 MW1-94 50 ACE 50 None 0Irgacure 500 2.5 MW1-95-8 MW1-94 30 None 0 SR-349 70 Irgacure 500 2.5MW1-95-9 MW1-94 30 ACE 35 SR-349 35 Irgacure 500 2.5 MW1-95-10 MW1-94 30ACE 70 None 0 Irgacure 500 2.5 MW1-96-1 MW1-91 100 None 0 None 0Irgacure 500 2.5 MW1-96-2 MW1-91 70 None 0 SR-349 30 Irgacure 500 2.5MW1-96-3 MW1-91 70 ACE 15 SR-349 15 Irgacure 500 2.5 MW1-96-4 MW1-91 70ACE 30 None 0 Irgacure 500 2.5 MW1-96-5 MW1-91 50 None 0 SR-349 50Irgacure 500 2.5 MW1-96-6 MW1-91 50 ACE 25 SR-349 25 Irgacure 500 2.5MW1-96-7 MW1-91 50 ACE 50 None 0 Irgacure 500 2.5 MW1-96-8 MW1-91 30None 0 SR-349 70 Irgacure 500 2.5 MW1-96-9 MW1-91 30 ACE 35 SR-349 35Irgacure 500 2.5 MW1-96-10 MW1-91 30 ACE 70 None 0 Irgacure 500 2.5MW1-102 MW1-101 70 HEA 15 SR-349 15 Irgacure 2959 2.5 MW2-C1 MW1-101 70ACE 15 SR-349 15 Irgacure 500 5 MW2-001A MW1-101 70 ACE 15 SR-349 15Irgacure 500 5 Irganox 1010 0.1 MW2-001B MW1-101 50 ACE 25 SR-349 25Irgacure 500 5 Irganox 1010 0.1 MW2-001C MW1-101 70 Phenoxyethyl 15Ebecryl 600 15 Irgacure 2959 5 Irganox 1010 0.1 acrylate MW2-001DMW1-101 50 Phenoxyethyl 25 Ebecryl 600 25 Irgacure 2959 5 Irganox 10100.1 acrylate MW2-001E MW1-101 70 Phenoxyethyl 6 Ebecryl 600 24 Irgacure2959 5 Irganox 1010 0.1 acrylate MW2-001F MW1-101 50 Phenoxyethyl 10Ebecryl 600 40 Irgacure 2959 5 Irganox 1010 0.1 acrylate MW2-001GMW1-101 70 Phenoxyethyl 15 TPGDA 15 Irgacure 2959 5 Irganox 1010 0.1acrylate MW2-001H MW1-101 50 Phenoxyethyl 25 TPGDA 25 Irgacure 2959 5Irganox 1010 0.1 acrylate MW2-001I MW1-101 70 Phenoxyethyl 15 3EO TMPTA15 Irgacure 2959 5 Irganox 1010 0.1 acrylate MW2-001J MW1-101 50Phenoxyethyl 25 3EO TMPTA 25 Irgacure 2959 5 Irganox 1010 0.1 acrylateMW2-001K MW1-101 70 Phenoxyethyl 15 TMPTA 15 Irgacure 2959 5 Irganox1010 0.1 acrylate MW2-001L MW1-101 50 Phenoxyethyl 25 TMPTA 25 Irgacure2959 5 Irganox 1010 0.1 acrylate

Many other benefits will no doubt become apparent from futureapplication and development of this technology.

All patents, published applications, and articles noted herein arehereby incorporated by reference in their entirety.

The present subject matter includes combinations of components andaspects of the various compositions described herein. Thus, for example,the present subject matter includes one or more components and/orfeatures of one embodiment combined with one or more other componentsand/or features of other embodiment(s).

As described hereinabove, the present subject matter solves manyproblems associated with previous strategies, systems, and/or devices.However, it will be appreciated that various changes in the details,materials, and arrangements of components, which have been hereindescribed and illustrated in order to explain the nature of the presentsubject matter, may be made by those skilled in the art withoutdeparting from the principle and scope of the claimed subject matter, asexpressed in the appended claims.

What is claimed:
 1. A cure in place pressure sensitive adhesiveconsisting of: 20-80 wt % of a pre-polymerized acrylic backbone basepolymer having a molecular weight (Mw) of 100,000 to 1,000,000; 0-30 wt% of tackifier; 5-40 wt % of at least one liquid reactive oligomer; 0-30wt % of at least one of an acrylic-epoxy functional component; 0-30 wt %epoxy functional olefin; 0-2 wt % of at least one of a metal chelatecrosslinker-catalyst and external catalyst; and at least one structuraldiluent, wherein the structural diluent is selected from the groupconsisting of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate(S-21), Bis[(3,4-epoxycyclohexyl)methyl]adipate (S-28), difunctionalbisphenol A/epichlorohydrin derived liquid epoxy resin (Epon 828),Bisphenol A epoxy resin having a weight per epoxide of 235-263 g/eg asmeasured by ASTM D1652(Epon 834),beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (A-186),gamma-glycidoxypropyltrimethoxysilane (A-187), glycidyl ester ofneodecanoic acid (EP-10), isocyanate-functional urethane acrylate(Desmolux D100), isocyanate-bearing urethane acrylate (Desmolux D200),aliphatic polyisocyanate (low-viscosity hexamethylene diisocyanate (HDI)biuret) (Desmodur N3200), aliphatic polyisocyanate (hexamethylenediisocyanate (HDI) biuret) (Desmodur N100), aliphatic polyisocyanate(hexamethylene diisocyanate (HDI) trimer) (Desmodur N3300),poly(propylene oxide) (PPO) oligomer having a molecular weight (Mw) ofless than 5,000 daltons, trimethylolpropane oxetane (TMPO),poly(ethylene oxide) (PEO) oligomer having a molecular weight (Mw) ofless than 5,000 daltons, ethyl hexyl oxetane (2EH oxetane), difunctionaloxetane, ethoxylated bisphenol A diacrylate of the following formula (7)in which n+m=3, ethoxylated trimethylolpropane triacrylate of thefollowing formula (8), bisphenol A diglycidyl ether diacrylate of thefollowing formula (9), 1,2-cyclic ethers, 1,3-cyclic ethers, 1,4-cyclicethers, anhydrides, lactones, lactams, cyclic ethers, siloxanes,oxazolines, oxalidines, and bismaleimides;


2. The adhesive of claim 1 wherein the acrylic backbone base polymer hasa Mw of 250,000 to 750,000.
 3. The adhesive of claim 1 wherein astimulus for promoting polymerization is selected from the groupconsisting of radiation, heat, moisture, pressure, ultrasound, chemicalexposure, and combinations thereof.
 4. The adhesive of claim 1 whereinthe acrylic backbone base polymer comprises an acrylic block basepolymer, the acrylic block base polymer comprising two functional endsegments and one non-reactive middle segment, the reactive segmentsinclude one or more monomers of the non-reactive segment.
 5. Theadhesive of claim 1 wherein the structural diluent is selected from thegroup consisting of3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (S-21),Bis[(3,4-epoxycyclohexyl)methyl]adipate (S-28), difunctional bisphenolA/epichlorohydrin derived liquid epoxy resin (Epon 828), Bisphenol Aepoxy resin having a weight per epoxide of 235-263 g/eg as measured byASTM D1652(Epon 834), beta-(3,4epoxycyclohexyl)ethyltrimethoxysilane(A-186), gamma-glycidoxypropyltrimethoxysilane (A-187), glycidyl esterof neodecanoic acid (EP10), isocynate-functional urethane acrylate(Desmolux D100), isocyanate-bearing urethane acrylate (Desmolux D200),aliphatic polyisocyanate (low-viscosity hexamethylene diisocynate (HDI)biuret) (Desmodur N3200), aliphatic polyisocyanate (hexamethylenediisocynate (HDI) biuret) (Desmodur N100), aliphatic polyisocyanate(hexamethylene diisocynate (HDI) trimer) (Desmodur N3300),poly(propylene oxide) (PPO) oligomer having a molecular weight (MW) ofless than 5,000 daltons, trimethylolpropane oxetane (TMPO),poly(ethylene oxide) (PEO) oligomer having a molecular weight (Mw) ofless than 5,000 daltons, ethyl hexyl oxetane (2EH oxetane), difunctionaloxetane, ethoxylated bisphenol A diacrylate of the following formula (7)in which n+m=3, ethoxylated trimethylolpropane triacrylate of thefollowing formula (8), bisphenol A diglycidyl ether diacrylate of thefollowing formula (9), 1,2-cyclic ethers, 1,3-cyclic ethers, 1,4-cyclicethers, butyrolactone, valerolactone, caprolactone, methy-butyrolactone,butyrolactam, valerolactam, caprolactam, cyclic ethers, siloxanes,oxazolines, oxalidines, bismaleimides,

and lactones of the following formulas (10)-(12)

wherein n is 4 or 5, h, i, k, and m are independently 1 or 2 and each Ris independently chosen from H or hydrocarbyl containing up to 12 carbonatoms.
 6. The adhesive of claim 1 wherein the at least one liquidreactive oligomer is a silane terminated polyether (STPE).
 7. Theadhesive of claim 4 wherein the non-reactive segment is non-reactivewith the reactive functional group of the reactive segments.
 8. Theadhesive of claim 1 wherein the acrylic backbone base polymer comprisesan acrylic block base polymer, the acrylic block base polymer comprisingone functional end segment and one non-reactive middle segment.
 9. Theadhesive of claim 8 wherein the non-reactive segment is non-reactivewith the reactive functional group of the reactive segment.
 10. Theadhesive of claim 8 wherein the reactive segment includes one or moremonomers of the non-reactive segment.
 11. A cure in place pressuresensitive adhesive comprising: 20-80 wt % of a pre-polymerized acrylicbase polymer having a molecular weight (Mw) of 100,000 to 1,000,000;0-30 wt % of tackifier; 5-40 wt % of at least one liquid reactiveoligomer, the at least one liquid reactive oligomer is a silaneterminated polyether (STPE); 0-30 wt % of at least one of anacrylic-epoxy functional component; 0-30 wt % epoxy functional olefin;0-2 wt % of at least one of a metal chelate crosslinker-catalyst andexternal catalyst; and at least one structural diluent, the structuraldiluent is selected from the group consisting of3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (S-21),Bis[(3,4-epoxycyclohexyl)methyl]adipate (S-28), difunctional bisphenolA/epichlorohydrin derived liquid epoxy resin (Epon 828), Bisphenol Aepoxy resin having a weight per epoxide of 235-263 g/eq as measured byASTM D1652 (Epon 834), beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane(A-186), gamma-glycidoxypropyltrimethoxysilane (A-187), glycidyl esterof neodecanoic acid (EP-10), isocyanate-functional urethane acrylate(Desmolux D100), isocyanate-bearing urethane acrylate (Desmolux D200),aliphatic polyisocyanate (low-viscosity hexamethylene diisocyanate (HDI)biuret) (Desmodur N3200), aliphatic polyisocyanate (hexamethylenediisocyanate (HDI) biuret) (Desmodur N100), aliphatic polyisocyanate(hexamethylene diisocyanate (HDI) trimer) (Desmodur N3300),poly(propylene oxide) (PPO) oligomer having a molecular weight (Mw) ofless than 5,000 daltons, trimethylolpropane oxetane (TMPO),poly(ethylene oxide) (PEO) oligomer having a molecular weight (Mw) ofless than 5,000 daltons, ethyl hexyl oxetane (2EH oxetane), difunctionaloxetane, trimethylolpropane triacrylate (TMPTA) of the following formula(5), tripropyleneglycol diacrylate (TPGDA) of the following formula (6),ethoxylated bisphenol A diacrylate of the following formula (7) in whichn+m=3, ethoxylated trimethylolpropane triacrylate of the followingformula (8), bisphenol A diglycidyl ether diacrylate of the followingformula (9), 1,2-cyclic ethers, 1,3-cyclic ethers, 1,4-cyclic ethers,anhydrides, lactones, lactams, cyclic ethers, siloxanes, oxazolines,oxalidines, and bismaleimides;


12. The adhesive of claim 11 wherein the acrylic backbone base polymerincludes an acrylic block base polymer, the acrylic block base polymerincluding two functional end segments and one non-reactive middlesegment.
 13. The adhesive of claim 12 wherein the non-reactive segmentis non-reactive with the reactive functional group of the reactivesegments.
 14. The adhesive of claim 12 wherein the reactive segmentsinclude one or more monomers of the non-reactive segment.
 15. Theadhesive of claim 11 wherein the acrylic backbone base polymer includesan acrylic block base polymer, the acrylic block base polymer includingone functional end segment and one non-reactive middle segment.
 16. Theadhesive of claim 15 wherein the non-reactive segment is non-reactivewith the reactive functional group of the reactive segment.
 17. Theadhesive of claim 15 wherein the reactive segment includes one or moremonomers of the non-reactive segment.